WO2010103998A1 - Connection sheet for solar battery cell electrode, process for manufacturing solar cell module, and solar cell module - Google Patents

Connection sheet for solar battery cell electrode, process for manufacturing solar cell module, and solar cell module Download PDF

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Publication number
WO2010103998A1
WO2010103998A1 PCT/JP2010/053604 JP2010053604W WO2010103998A1 WO 2010103998 A1 WO2010103998 A1 WO 2010103998A1 JP 2010053604 W JP2010053604 W JP 2010053604W WO 2010103998 A1 WO2010103998 A1 WO 2010103998A1
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Prior art keywords
solar cell
sheet
wiring member
electrode
heating
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PCT/JP2010/053604
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French (fr)
Japanese (ja)
Inventor
畔地　秀一
櫻井　郁男
昌克 堀田
橋本　毅
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信越化学工業株式会社
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Application filed by 信越化学工業株式会社 filed Critical 信越化学工業株式会社
Priority to JP2011503789A priority Critical patent/JP5644759B2/en
Priority to EP10750752.7A priority patent/EP2408014A4/en
Priority to US13/255,848 priority patent/US20120012153A1/en
Priority to CN201080018484.2A priority patent/CN102414831B/en
Publication of WO2010103998A1 publication Critical patent/WO2010103998A1/en
Priority to US14/173,441 priority patent/US20140150844A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/02016—Circuit arrangements of general character for the devices
    • H01L31/02019—Circuit arrangements of general character for the devices for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02021—Circuit arrangements of general character for the devices for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
    • H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a solar cell electrode connection sheet and a method of manufacturing a solar cell module using the same, and more specifically, an electrode for taking out electric power of a solar cell and a wiring member are made of a conductive adhesive material, In particular, it is used when connecting by heating and pressurizing via a conductive resin adhesive, has good heat resistance, little degradation even when crimped at high temperatures, and against mechanical stress
  • the present invention relates to a sheet for connecting solar cell electrodes, which is a polymer sheet having good durability, and a method for producing a solar cell module using the sheet, and further, there is no problem of warping or cracking obtained thereby.
  • the present invention relates to a solar cell module.
  • a conductive wiring member is connected to the electrode of the solar cell.
  • a wiring member having a flat copper foil surface coated with solder is used, and the electrode of the solar battery cell and the wiring member are connected by solder (Patent Documents 1 and 2: Japanese Patent Laid-Open No. 2004-2005). -204256, 2005-50780).
  • solder connection requires a relatively high temperature, and stress is applied to the connection part due to the difference in the thermal contraction rate of the semiconductor structure part that is responsible for power generation, the electrode part and the solder, and the electrode member. Or cause cracks.
  • Patent Documents 3 to 6 JP-A-2006-54355, JP-A-2005-191200, JP-A-2005-302902, JP-A-61). -284974).
  • Patent Documents 7 to 11 JP-A-2005-101519). 2007-158302, 2007-214533, 2008-294383, 2008-300403).
  • Patent Document 15 Japanese Patent Laid-Open No. 7-11010
  • Patent Document 16 Japanese Patent Application Laid-Open No. 2003-261769
  • Patent Document 17 Japanese Patent No. 3169501.
  • Patent Documents 18 to 22 Japanese Patent Laid-Open Nos. 3-14873, 2000-63670, 2007-138100, 2007-171946, 2007-31628.
  • these do not consider application to the silicone rubber sheet used in the connection process between the solar cell electrodes and wiring members, and solve the problem of warping and cracking of the solar cells. There was no optimization to do that.
  • JP 2004-204256 A Japanese Patent Laid-Open No. 2005-50780 JP 2006-54355 A JP-A-2005-191200 JP 2005-302902 A JP-A 61-284773 JP 2005-101519 A JP 2007-158302 A JP 2007-214533 A JP 2008-294383 A JP 2008-300403 A JP-A-5-198334 JP-A-6-36853 JP-A-6-289352 JP 7-11010 A JP 2003-261769 A Japanese Patent No. 3169501 JP-A-3-14873 JP 2000-63670 A JP 2007-138100 A JP 2007-171946 A JP 2007-31628 A
  • the present invention has been made in view of the above circumstances, and when connecting the electrode and the wiring member for taking out the electric power of the solar battery cell by heating and pressurizing via the conductive adhesive, the heating and pressurizing member, It is used by interposing between wiring members, has high heat resistance and durability, and does not stick to solder or metal of wiring members, etc., and can produce high quality solar cells and solar cell modules. It is an object of the present invention to provide a solar cell electrode connection sheet that is made possible, a method for manufacturing a solar battery module using the connection sheet, and a solar battery module obtained thereby.
  • the present inventors have connected the solar cell electrode and the wiring member by heating and pressurizing via a conductive adhesive, particularly a conductive resin adhesive.
  • a conductive adhesive particularly a conductive resin adhesive.
  • the compression set of the polymer sheet is reduced. Therefore, it was found that deterioration due to permanent deformation based on pressure bonding can be reduced. Therefore, by using the solar cell electrode connection sheet, which is an optimized polymer sheet, in the manufacturing process of solar cells and solar cell modules consisting of a single cell, the power generation efficiency is reduced due to poor contact. It is easy to heat and pressure bond the conductive adhesive material satisfactorily, and can be connected by repeatedly using the same part of the sheet without sticking to the wiring member or conductive adhesive etc. As a result, the inventors have made the present invention.
  • the present invention provides the following solar cell electrode connection sheet, solar cell module manufacturing method, and solar cell module.
  • [Claim 1] Polymer used by interposing between the heating and pressure member and the wiring member when connecting the electrode and wiring member for taking out the electric power of the solar cell by heating and pressing the conductive adhesive material.
  • a sheet for connecting solar cell electrodes characterized by being a sheet.
  • [Claim 2] The solar cell electrode electrode connection sheet according to claim 1, wherein the polymer sheet contains one or more selected from a heat-resistant resin, fluororubber and silicone rubber.
  • the solar cell connection sheet according to claim 2 wherein the heat-resistant resin is at least one selected from a fluororesin and a polyamide-based resin having a glass transition temperature of 200 ° C or higher or a melting point of 300 ° C or higher.
  • the heat-resistant resin is at least one selected from a fluororesin and a polyamide-based resin having a glass transition temperature of 200 ° C or higher or a melting point of 300 ° C or higher.
  • the polymer sheet is reinforced with a cloth and / or fiber made of an inorganic material and / or a heat resistant resin.
  • the polymer sheet contains a thermally conductive filler made of one or more inorganic substances selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon allotropes.
  • the sheet seat for connection of the photovoltaic cell electrode of any one of these.
  • the polymer sheet is (A) Crosslinkable organopolysiloxane having an average degree of polymerization of 100 or more: 100 parts by mass, (B) at least one heat conductive powder selected from metal, metal oxide, metal nitride, metal carbide, metal hydroxide and carbon allotrope: 0 to 600 parts by mass; (C) Carbon black powder: 0 to 80 parts by mass, (D) Reinforcing silica powder having a BET specific surface area of 50 m 2 / g or more: 0 to 50 parts by mass;
  • a curing agent is a silicone rubber sheet obtained by forming a silicone rubber composition containing an effective amount of curing into a sheet and curing it by heating.
  • thermo conductive powder as the component (B) is a metal silicon powder having an average particle diameter of 1 to 50 ⁇ m blended in an amount of 5 parts by mass or more.
  • the thermal conductive powder as component (B) is a crystalline silicon dioxide powder blended in an amount of 5 parts by mass or more and having an average particle size of 1 to 50 ⁇ m.
  • connection sheet for solar cell electrodes according to any one of claims 1 to 17, wherein the conductive adhesive material is in a film form.
  • connection sheet for solar cell electrodes according to any one of claims 1 to 17, wherein the conductive adhesive material is in a film form.
  • the electrode for taking out the electric power of the solar battery cell and the wiring member are connected by heating and pressing the conductive adhesive material between the heating and pressing member and the wiring member.
  • a method for manufacturing a solar cell module comprising heating and pressurizing the sheet for connection according to any one of the preceding claims.
  • an optimized solar cell electrode made of a polymer sheet is used to connect an electrode for taking out electric power of a solar cell and a wiring member by heating and pressurizing via a conductive adhesive material. Since the connecting sheet is interposed between the heating and pressure member and the wiring member, the entire surface of the heated / pressurized part can be pressure-bonded at a uniform temperature and pressure. As a result, there is no contact failure, a reliable connection is possible, a solar cell consisting of a single solar cell with high quality and good long-term durability, and a solar cell with a structure in which a plurality of solar cells are arranged and connected Battery modules can be manufactured stably and supplied to the market.
  • the solar battery cell and the solar battery module that have solved the problem of warping and cracking of the solar battery cell It can be manufactured stably and supplied to the market. In the future, it is predicted that the thinning of solar cells will progress, and a greater effect can be expected.
  • the sheet for connecting solar cell electrodes according to the present invention prevents sticking between the conductive adhesive material and the heating and pressing member that protrudes during pressure bonding, or the conductive adhesive material is deposited on the heating and pressing member. There is also an effect to prevent this.
  • the connecting sheet Since the heating and pressurizing members are usually hard metal, the connecting sheet also plays a role of mitigating the impact from the heating and pressurizing members at the time of pressure bonding and preventing cracking of the solar cells.
  • the sheet for connecting solar cell electrodes of the present invention has a non-adhesive property to members such as a wiring member, a conductive adhesive material, and a surface electrode that are in contact with each other at the time of crimping. Repetitive crimping is possible, and a reliable connection with reduced cost and labor saving is possible.
  • a is a plan view
  • b is a cross-sectional view
  • c is an enlarged cross-sectional view of a solar battery cell.
  • the electrode connecting sheet of the present invention when connecting the electrode for taking out the power of the solar battery cell and the wiring member by heating and pressing through the conductive adhesive material, the heating and pressing member and the wiring member
  • the polymer sheet is preferably a polymer sheet containing at least one selected from a heat-resistant resin, fluororubber and silicone rubber.
  • Type of solar cell The type of solar cell in which the solar cell electrode connection sheet of the present invention is used is not particularly limited as long as an electrode for taking out electric power is provided,
  • Examples of the material that photoelectrically converts the sunlight to generate electric power include silicon-based, compound-based, and organic-based materials.
  • silicon a single crystal silicon type, a polycrystalline silicon type, a microcrystalline silicon type, an amorphous silicon type, a hybrid type of crystalline silicon and amorphous silicon (HIT type), and the like can be given.
  • a group III-V group such as a GaAs single crystal, a group consisting of a group I-III-V compound called a CIS system (calcopalite system), for example, Cu (In, Ga) Se 2 , Cu (In, Ga) (Se, S) 2 , CuInS 2, etc., which are called CIGS, CIGSS, CIS, CdTe—CdS system, etc., respectively.
  • a dye-sensitized type, an organic thin film type, and the like are exemplified.
  • a relatively thick crystalline solar cell and a thin film solar cell thinly formed on glass or a film can be exemplified.
  • a collecting electrode called a finger or a bus bar may be formed with silver as a main component, and in particular, a collecting electrode is provided.
  • the wiring member is preferably a strip-shaped conductive member having a flat cross section, and the material is selected from the group consisting of Cu, Ag, Au, Fe, Ni, Zn, Co, Ti, Pb and Mg. Those containing one or more selected metal elements are preferred.
  • the wiring member covered with solder may be used.
  • a conductive resin adhesive containing an insulating resin and conductive particles is suitable, and it can be used in the form of a paste, but it is manufactured by using a film-shaped material. This is preferable because the process can be simplified. Furthermore, what was previously formed on the wiring member can also be used.
  • the insulating resin used for the conductive adhesive material can be selected from an epoxy resin, an acrylic resin, a phenoxy resin, a polyimide resin, a silicone resin, a urethane resin, or a modified one thereof, or a mixture thereof. However, the present invention is not limited to these.
  • thermosetting epoxy resin or an acrylic resin containing an acrylic rubber or butyl rubber component and a dynamic viscoelastic modulus of 1 ⁇ 10 3 to 1 ⁇ 10 10 Pa can be used.
  • solder can be used as the conductive adhesive material.
  • the conductive particles used by mixing with the resin adhesive include Cu, Ag, Au, Fe, Ni, Zn, Co, Ti, Pb, Mg, solder and other particles, styrene and other resins, glass and silica particles.
  • Examples thereof include metal particles such as particles obtained by plating a metal selected from the above metals on the surface, and the average particle size of these particles is preferably 1 to 100 ⁇ m, more preferably 2 to 80 ⁇ m.
  • the average particle diameter can be obtained as a cumulative weight average value D 50 (or median diameter) or the like using a particle size distribution measuring apparatus by a laser diffraction method.
  • the sheet for connecting solar cell electrode of the present invention is obtained by heating and curing a conductive resin adhesive material containing an insulating resin and conductive particles or by melting solder. In general, it is used in contact with the heating / pressurizing member of the wiring member connecting apparatus that is usually heated to 300 ° C. or higher.
  • the polymer material is preferably. Specifically, it is at least one polymer selected from a heat-resistant resin, fluororubber, and silicone rubber.
  • the heat resistant resin is preferably at least one selected from fluororesins and polyamide resins having a glass transition temperature of 200 ° C. or higher or a melting point of 300 ° C. or higher.
  • the upper limit value of the glass transition temperature or melting point of the heat resistant resin is not particularly limited, but it is usually preferably 500 ° C. or lower.
  • fluororesins having a melting point of 300 ° C. or more include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polytrifluoroethylene chloride (PTFCE), polyvinylidene fluoride ( PVDF) and the like, but are not limited thereto.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • PPFCE polytrifluoroethylene chloride
  • PVDF polyvinylidene fluoride
  • the polyamide resin having a glass transition temperature of 200 ° C. or higher include aromatic polyimide, polyamideimide, aromatic polyamide, polyethersulfone, and polyetherimide, but are not limited thereto.
  • a resin-based sheet such as a heat-resistant sheet impregnated with aramid fibers can also be exemplified.
  • the solar cell electrode connection sheet of the present invention preferably has a high thermal conductivity to some extent because it is necessary to transfer heat from the heating / pressurizing member to the conductive adhesive member. Since the thermal conductivity of the polymer material is relatively low, it is preferable to increase the thermal conductivity of the sheet by adding a thermally conductive filler made of an inorganic substance into the polymer material.
  • the thermally conductive filler made of an inorganic material is preferably one or more materials selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon allotropes.
  • the heat conductive filler made of metal is preferably one or more metal powders selected from metal silicon, aluminum, gold, silver, copper, iron, nickel, and alloys thereof.
  • metal oxides include zinc oxide, aluminum oxide, magnesium oxide, silicon dioxide, and iron oxide.
  • metal nitrides include boron nitride, aluminum nitride, and silicon nitride.
  • metal carbides include silicon carbide and boron carbide.
  • metal hydroxide examples of the carbon allotrope include various carbon fibers and graphite. The blending amount of these thermally conductive fillers is preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the polymer material.
  • the main characteristics required for the solar cell electrode connection sheet of the present invention include cushioning properties, heat-resistant pressure bonding properties, and thermal conductivity. Silicone rubber is particularly easy to adjust the elongation and hardness so as to have an appropriate cushioning property, has good heat-resistant pressure-bonding properties, and can add heat conductive filler to increase thermal conductivity. It is suitable as a material for the connection sheet of the solar battery cell electrode of the present invention.
  • silicone rubber composition used in the present invention for example, (A) An organopolysiloxane having an average degree of polymerization of 100 or more and (E) a curing agent, and if necessary, from (B) an allotrope of metal, metal oxide, metal nitride, metal carbide, metal hydroxide and carbon At least one thermally conductive powder selected; (C) carbon black powder, (D) The thing formed by mix
  • (A) component The crosslinkable organopolysiloxane having an average degree of polymerization of 100 or more, which is the component (A) used in the present invention, is represented by the following average composition formula (1), for example.
  • R n SiO (4-n) / 2 (1) In the formula (1), n represents a positive number of 1.9 to 2.4, and R represents a substituted or unsubstituted monovalent hydrocarbon group.
  • substituted or unsubstituted monovalent hydrocarbon group represented by R include alkyl groups such as methyl group, ethyl group and propyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, vinyl group and allyl group.
  • alkyl groups such as methyl group, ethyl group and propyl group
  • cycloalkyl groups such as cyclopentyl group and cyclohexyl group
  • vinyl group and allyl group examples include aryl groups such as alkenyl groups, phenyl groups, tolyl groups, etc., or halogenated hydrocarbon groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine atoms or fluorine atoms. Is done.
  • the main chain is composed of dimethylsiloxane units, or an organic group such as methyl group, vinyl group, phenyl group or trifluoropropyl group is introduced into the main chain of this organopolysiloxane.
  • an organic group such as methyl group, vinyl group, phenyl group or trifluoropropyl group is introduced into the main chain of this organopolysiloxane.
  • Those are preferred.
  • 0.0001 to 10 mol% of the organic group is a vinyl group and 80 mol% or more is a methyl group.
  • those having molecular chain ends blocked with triorganosilyl groups or hydroxyl groups are preferred.
  • the triorganosilyl group include a trimethylsilyl group, a dimethylvinylsilyl group, and a trivinylsilyl group.
  • the organopolysiloxane of component (A) may be used alone or as a mixture of a plurality of types, but the organopolysiloxane molecule of component (A) represented by the above formula (1) It is preferable that 0.10 to 0.50 mol% of all R in the whole is a vinyl group. Moreover, in this invention, it is preferable that the average degree of polymerization of (A) component represented by (1) Formula is 100 or more, especially 200 or more. If the average degree of polymerization is less than 100, the mechanical strength after curing may be inferior.
  • the upper limit of the average degree of polymerization is not particularly limited, but is preferably 100,000 or less, particularly preferably 50,000 or less.
  • an average degree of polymerization is a polystyrene conversion value by gel permeation chromatography (GPC).
  • the component (B) component is added to give thermal conductivity, and is used when high thermal conductivity is required.
  • This is at least one heat conductive powder selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides and allotropes of carbon, and provides heat conductivity to the silicone rubber sheet of the present invention. It is a filler to be applied. Specific examples of these include gold, silver, copper, iron, metal silicon, nickel, aluminum and alloys thereof as metals, and zinc oxide, aluminum oxide, magnesium oxide, silicon dioxide, iron oxide as metal oxides.
  • metal nitrides include boron nitride, aluminum nitride, and silicon nitride; metal carbides such as silicon carbide and boron carbide; metal hydroxides such as aluminum hydroxide; and carbon allotropes such as various carbons. Examples thereof include fibers and graphite, but are not limited thereto.
  • metal silicon powder and crystalline silicon dioxide powder are particularly suitable.
  • both powders have a low specific gravity, and the specific gravity of the sheet can be reduced, so that the handleability of the silicone rubber sheet for thermocompression bonding is improved.
  • the shape of these powders may be any of spherical, oval, flat, angular irregular shape, round irregular shape, needle shape, etc., and is not particularly limited.
  • spherical shapes, irregular shapes by pulverization, and the like can be exemplified.
  • the purity of the heat conductive powder is not particularly limited, but is preferably 50% by mass or more, particularly 80% by mass or more, more preferably 95% by mass or more from the viewpoint of imparting thermal conductivity. It is.
  • the method for producing the metal silicon powder used in the present invention is not particularly limited, but a product obtained by reducing silica into metal silicon by pulverization with an existing crusher or pulverizer such as a ball mill. , Pulverized metal silicon (wafer) generated from semiconductor manufacturing processes, etc., and powdered by pulverization method, and metal silicon melted at high temperature to be micronized by gas phase method, Spherical metal silicon powders such as those that have been cooled and solidified into spherical particles (here “spherical” or “spherical” means a smooth shape with no sharp edges on the surface of each particle)
  • the ratio of major axis / minor axis is 1.0 to 1.4, preferably about 1.0 to 1.2).
  • the purity of the finely divided metal silicon powder is not particularly limited, but is preferably 50% by mass or more (ie, 50 to 100% by mass) from the viewpoint of imparting thermal conductivity, and more preferably 80% by mass. It is desirable that the amount is 80% to 100% by mass, more preferably 95% by mass or more (95% to 100% by mass).
  • High-purity metallic silicon powder has no defects in the natural oxide film on the surface and has good high-temperature thermal stability. In order to provide an oxide film, it is preferable to perform heat treatment at 100 ° C. or higher for 1 hour or longer while air-flowing in the powder fluidized bed.
  • the average particle size of the component (B) metal silicon powder or crystalline silicon dioxide powder used in the present invention is 50 ⁇ m or less, preferably 1 to 50 ⁇ m, more preferably 1 to 25 ⁇ m, especially 2 to 25 ⁇ m. Is used. Particles having an average particle size of less than 1 ⁇ m are difficult to manufacture and may be difficult to mix in large quantities. If the particle size exceeds 50 ⁇ m, the mechanical strength of the rubber cured product may be impaired. There may be a problem in the surface performance of the sheet.
  • the average particle diameter can be determined as a cumulative weight average value D 50 (or median diameter) or the like using a particle size distribution measuring apparatus such as a laser light diffraction method.
  • the component (B) metal silicon powder is a silane coupling agent or a partial hydrolyzate thereof, an alkylalkoxysilane or a part thereof for the purpose of improving the thermal stability of the silicone rubber composition and the compounding property of the powder. It may be surface-treated with a hydrolyzate, an organic silazane, a titanate coupling agent, an organopolysiloxane oil, a hydrolyzable functional group-containing organopolysiloxane, or the like. In these treatments, the inorganic powder itself may be treated in advance, or may be treated at the time of mixing with the component (A).
  • the blending amount of the component (B) may be 0 to 600 parts by mass with respect to 100 parts by mass of the component (A), but it is particularly preferably used in the range of 5 to 400 parts by mass. If the amount is more than 600 parts by mass, blending becomes difficult, the moldability becomes worse, and the strength of the sheet may be weakened.
  • Component (C) The carbon black powder, which is the component (C) used in the present invention, improves the heat resistance by improving the mechanical strength of the silicone rubber sheet, particularly the mechanical strength during heating, and also makes it thermally conductive and conductive. It is used when imparting antistatic properties due to.
  • Carbon black is classified into furnace black, channel black, thermal black, acetylene black, etc. depending on the production method, and usually contains many impurities such as sulfur.
  • acetylene black is preferable because it has few impurities.
  • the method for measuring volatile components other than water is described in “Testing method of carbon black for rubber” in JIS K 6221. Specifically, a specified amount of carbon black is put in a crucible, and the volatilization loss after heating at 950 ° C. for 7 minutes is measured.
  • the average particle size of the carbon black as the component (C) is preferably in the range of 10 to 300 nm, particularly preferably in the range of 15 to 100 nm.
  • the BET specific surface area is preferably 20 to 300 m 2 / g, and particularly preferably 30 to 200 m 2 / g.
  • the shape of carbon black may be either powder or needle.
  • the average particle diameter of carbon black is an average particle diameter obtained by so-called electron microscopy, in which the primary particle diameter is measured from a photograph taken using an electron microscope, and the obtained particle diameter is arithmetically averaged.
  • Carbon black usually aggregates primary particles to form secondary particles, but the average particle size referred to here is not the average particle size of the secondary particles but the average particle size of the primary particles.
  • the blending amount of the component (C) is 0 to 80 parts by weight with respect to 100 parts by weight of the component (A), and is preferably used in the range of 5 to 75 parts by weight. If it exceeds 80 parts by mass, it may be difficult to mix uniformly, and the molding processability of the resulting composition may be extremely deteriorated.
  • (D) component As the reinforcing silica powder having a BET specific surface area of 50 m 2 / g or more, which is the component (D) used in the present invention, hydrophilic or hydrophobic fumed silica (dry silica), precipitated silica (wet silica) , Crystalline silica, quartz and the like, and these can be used alone or in combination of two or more. Fumed silica and precipitated silica preferably have a BET specific surface area of 50 m 2 / g or more from the viewpoint of reinforcement, but usually have a BET specific surface area of 50 to 800 m 2 / g, particularly about 100 to 500 m 2 / g. Good to use. When the specific surface area is less than 50 m 2 / g, the reinforcing effect may not be sufficiently obtained.
  • hydrophilic silicas include Aerosil 130, 200, 300 (Nippon Aerosil Co., Ltd. or Degussa product name), Cabosil MS-5, MS-7 (manufactured by Cabot). Product name), Rheorosil QS-102,103 (product name manufactured by Tokuyama Co., Ltd.), NipsilLP (product name manufactured by Nippon Silica Kogyo Co., Ltd.), and the like.
  • Hydrophobic silica includes Aerosil R-812, R-812S, R-972, R-974 (trade name manufactured by Degussa), Rheorosil MT-10 (trade name manufactured by Tokuyama Corporation), and Nippon Sil series (Japan). The product name is manufactured by Silica Industry Co., Ltd.), but is not limited thereto.
  • the blending amount of the component (D) in the present invention is 0 to 50 parts by mass with respect to 100 parts by mass of the component (A), more preferably 5 to 35 parts by mass, particularly 10 to 30 parts by mass. Preferably there is. If it exceeds 50 parts by mass, the plasticity of the silicone rubber composition may become too high, resulting in poor moldability, or the cured rubber may become too hard.
  • the curing agent which is the component (E) used in the present invention can be appropriately selected from known ones usually used for curing silicone rubber.
  • a curing agent for example, a) organic peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide used in radical reactions; b) When the organopolysiloxane of component (A) has an alkenyl group, an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule as an addition reaction curing agent, and platinum And combinations with platinum group metal catalysts such as palladium; and the like.
  • the addition reaction curing agent b) is preferable because the reaction is easy to control and no reaction residue remains, but both may be used together if necessary.
  • the addition amount of these curing agents may be the same as in the case of ordinary silicone rubber, but is generally as follows.
  • the curing agent a) is preferably used in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A) organopolysiloxane.
  • the amount of hydrogen atoms bonded to the atoms is 0.5 to 5 mol
  • the amount of the platinum group metal catalyst is 0.1 to 1,000 ppm (mass basis) as a metal component with respect to the component (A). ) Is preferred.
  • silicone rubber composition of the present invention if necessary, heat resistance imparting agents such as cerium oxide, bengara and titanium oxide, fillers such as clay, calcium carbonate, diatomaceous earth and titanium dioxide, low molecular siloxane esters, Dispersants such as silanol, adhesion imparting agents such as silane coupling agents, titanium coupling agents, platinum group metal compounds that impart flame retardancy, tetrafluoropolyethylene particles that increase the green strength of rubber compounds, glass fibers, aramid fibers Reinforcing fibers such as may be added.
  • heat resistance imparting agents such as cerium oxide, bengara and titanium oxide
  • fillers such as clay, calcium carbonate, diatomaceous earth and titanium dioxide, low molecular siloxane esters
  • Dispersants such as silanol
  • adhesion imparting agents such as silane coupling agents, titanium coupling agents, platinum group metal compounds that impart flame retardancy, tetrafluoropolyethylene particles that increase the green strength of rubber compounds, glass
  • the silicone rubber composition used in the present invention may be prepared by kneading the above-described components using a mixer such as a two-roll mill, a kneader, a Banbury mixer, or a planetary mixer. It is preferable to knead the other components in advance so that it may be added immediately before use.
  • a silicone rubber sheet which is a solar cell electrode connection sheet of the present invention
  • a silicone rubber composition containing all components up to a curing agent is dispensed to a predetermined thickness with a calendar or an extruder. And a method of curing after coating a film with a liquid silicone rubber composition or a silicone rubber composition dissolved in a solvent such as toluene and liquefied.
  • the elongation and hardness at the time of cutting after curing of the silicone rubber composition have the following characteristics.
  • the elongation at cutting at a room temperature of 23 ° C. is preferably 40 to 1,000%, and more preferably 60 to 300%. Particularly preferred is 70 to 150%.
  • the elongation should be small in order to avoid misalignment of the connecting member, but if the elongation is less than 40%, the sheet lacks flexibility. The sheet cannot be pressed with a uniform pressure without being able to follow, and the stress cannot be dispersed, making it easy to break, or the sheet breaks when a force in the bending direction is applied to the sheet. May occur.
  • the hardness at room temperature of 23 ° C. measured with a type A durometer is preferably 10 to 90, and particularly preferably 40 to 85. This hardness is compatible with cushioning for transmitting a uniform pressure by correcting the tolerance of flatness, flatness, or parallelism of the object to be pressed together with preventing displacement.
  • the solar cell electrode connection sheet described above may be reinforced with a cloth and / or fiber made of an inorganic material and / or a heat-resistant resin.
  • a cloth and / or fiber made of an inorganic material and / or a heat-resistant resin For example, glass fibers, carbon fibers, stainless fibers, etc. are used as the fibers made of inorganic materials, and fluororesin fibers such as aramid fibers, amide fibers, tetrafluoropolyethylene, etc. are used as the fibers made of the heat resistant resin. It is not limited to.
  • these fibers may be kneaded in a polymer, or a cross made by knitting these fibers may be laminated on an intermediate layer or one side, and is limited to these methods. is not.
  • Reinforcement with fiber material suppresses the elongation in the surface direction of the sheet, and can reliably transmit the pressure from the heating / pressurizing member of the wiring member connecting device to the conductive adhesive member, and also has a great resistance to tearing. To improve.
  • the solar cell electrode connection sheet of the present invention is in direct contact with the heating / pressurizing member of the wiring member connecting device, the wiring member, the protruding conductive adhesive material, etc. during heating / pressurization.
  • the conductive adhesive material a material containing an insulating resin and conductive particles, or solder is used.
  • the solar cell electrode connection sheet used at the time of heating and pressure bonding is often used at a high temperature of 300 ° C. or more, and may be stuck to these directly contacting members and torn. It is preferable to have non-adhesiveness without adversely affecting various members that are in direct contact.
  • Thermal conductivity of solar cell electrode connection sheet The solar cell electrode connection sheet of the present invention has a role of transferring heat from the heating / pressurizing member of the wiring member connecting device to the conductive adhesive material. From this viewpoint, it is preferable that the thermal conductivity is high.
  • the thermal conductivity at room temperature of 23 ° C. is preferably 0.3 W / mK or more, more preferably 0.4 W / mK or more, and particularly preferably 0.6 W / mK or more. If it is lower than 0.3 W / mK, it is difficult for heat to be transferred to the conductive adhesive material, so the temperature of the heating / pressurizing member must be raised.
  • the burden on the wiring member connecting device becomes heavy, and the cost merit of this connection method may be lost.
  • a higher temperature heating / pressurizing member comes into contact with the solar cell electrode electrode connection sheet, thermal deterioration of the sheet may be promoted.
  • the high-temperature heating / pressurizing member gives radiant heat to the conductive electrode film on the semiconductor element, it may cause a problem in the solar battery cell.
  • the thermal conductivity exceeds 5 W / mK, blending of the thermal conductive powder becomes difficult, and the sheet strength becomes too weak to withstand use, so that it is preferably 5 W / mK or less.
  • the solar cell electrode connection sheet of the present invention can also have a structure in which two or more types of sheet layers having different compositions are laminated from the solar cell electrode connection sheet of the present invention.
  • sheet layers having different compositions
  • seat which is not reinforced may be laminated
  • the thickness of the solar cell electrode connection sheet of the present invention is preferably 0.01 to 1 mm.
  • the material is a heat-resistant resin, it is preferably 0.01 to 0.5 mm, particularly preferably 0.02 to 0.2 mm. If the thickness is less than 0.01 mm, the strength is too weak and easily broken, and the handleability may be deteriorated. On the other hand, if the thickness exceeds 0.5 mm, the way of heat transfer may deteriorate.
  • the material of the sheet is fluororubber or silicone rubber, the thickness is 0.05 to 1 mm, particularly preferably 0.1 to 0.5 mm. If the thickness is less than 0.05 mm, the cushioning property is not sufficient, and uniform pressure transmission may be impossible.
  • the thickness of the solar cell electrode connection sheet of the present invention is as thin as 0.01 to 0.2 mm, even if the thermal conductivity is less than 0.3 W / mK, the required sheet thickness direction Since heat conduction performance may be ensured, the heat conductivity is not necessarily 0.3 W / mK or more.
  • the solar cell electrode connection method of the present invention is a wiring member connection in the step of connecting the electrode and the wiring member for taking out the electric power of the solar cell by heating and pressurizing via a conductive adhesive material. Heating and pressurization are performed by interposing the solar cell electrode connection sheet of the present invention between the heating and pressurizing member of the apparatus and the wiring member.
  • the conductive adhesive material is prepared separately in the form of a film or paste containing an insulating resin and conductive particles, and placed on the electrode member for taking out the electric power of the solar battery cell before connection. You may use, and you may use what shape
  • the plating solder can be used as a conductive adhesive material without using another conductive adhesive material.
  • it may be connected under the condition that the solder does not melt by using a conductive resin adhesive material containing an insulating resin and conductive particles. Further, both the insulating resin and the conductive adhesive material containing conductive particles may function as a conductive adhesive material and may be connected in combination.
  • connection method of the present invention uses the optimized solar cell electrode connection sheet according to the present invention interposed between the heating and pressure member and the wiring member, so that the entire surface of the heating and pressure member is uniform. It can be pressure-bonded at various temperatures and pressures, and can prevent sticking between the protruding conductive adhesive material and the heating and pressing member, or prevent the conductive adhesive material from depositing on the heating and pressing member. It becomes possible.
  • the heating and pressing members are usually hard metal, the connecting sheet plays a role of mitigating the impact from the heating and pressing members during crimping and preventing cracking of the solar cells. You can also.
  • connection condition of the solar cell electrode of the present invention is optimized by the type and structure of the solar cell and the conductive adhesive material matched to the solar cell electrode, but the conductive resin adhesive material containing the insulating resin and conductive particles is used.
  • the heating temperature of the conductive resin adhesive material is 130 to 220 ° C.
  • the temperature of the heating and pressurizing member is 200 to 400 ° C.
  • the pressure is 1 to 5 MPa
  • the pressure bonding time is Although it is 3 to 30 seconds, it is not limited to this range.
  • connection between the electrode of the solar battery cell and the wiring member may be performed separately for each electrode and the wiring member, but a front electrode and a back electrode for taking out electric power from the solar battery cell are provided.
  • the method of simultaneously heating and pressurizing the front surface electrode and the wiring member, and the back surface electrode and the other wiring member is preferable because the production efficiency is improved.
  • the solar cell module of the present invention has a single or multiple solar cells arranged, and an electrode and a wiring member for taking out the electric power of the solar cells adjacent to each other are the solar cell electrodes of the present invention. Connected according to the connection method.
  • the solar cell module of the present invention is a process of connecting an electrode for extracting electric power of a solar battery cell and a wiring member by heating and pressurizing via a conductive adhesive material. It is manufactured with a sheet for connecting solar cell electrodes optimized in between, and has, for example, the structure shown in FIG.
  • FIG. 2a is a plan view showing an example of a solar cell connection (a part of the solar cell module)
  • b is a cross-sectional view
  • c is a cross-sectional enlarged view of the solar cell
  • 1 is a silicon substrate
  • 2 is an electrode
  • 3 is a conductive adhesive material
  • 4 is a wiring member
  • 10 is a solar cell.
  • the entire surface of the heating / pressurizing part can be crimped at a uniform temperature / pressure, and the solar cell module obtained by the present invention has no contact failure, high quality and good long-term durability.
  • a solar battery cell free from warping or cracking can be obtained.
  • Example 1 to 6 The following components were blended in the proportions (mass parts) shown in Table 1 to obtain a solar cell electrode connection sheet.
  • A Organopolysiloxane: (A-1) Methylvinyl consisting of 99.85 mol% of dimethylsiloxane units and 0.15 mol% of methylvinylsiloxane units, having an average degree of polymerization of 8,000, and having both molecular chain ends blocked with dimethylvinylsiloxy groups Polysiloxane (a-2) Consisting of 99.5 mol% of dimethylsiloxane units and 0.5 mol% of methylvinylsiloxane units, the average degree of polymerization was 8,000, and both ends of the molecular chain were blocked with dimethylvinylsiloxy groups Methyl vinyl polysiloxane
  • B Thermally conductive filler: (B-1) Metallic silicon pulverized powder having an average particle size of 5 ⁇ m (surface subjected
  • composition was prepared as described below and molded into a sheet.
  • component (D) When component (D) is blended, component (f-1) and ion-exchanged water are used as a surface treatment agent for component (A), component (D) and component (D) at 170 ° C. using a kneader. The mixture was kneaded and kneaded while heating for 2 hours. When the component (D) is zero, this step is not performed. Add component (B), component (C) and component (g-1) as necessary to the resulting mixture or component (A) and blend and knead for 15 minutes using a pressure kneader. Homogenized.
  • the components (e-1), (h-1), and (e-2) are added in the above order while kneading sequentially with a two-roll mill, and cured.
  • a functional silicone rubber composition was prepared.
  • the (e-3) or (e-4) component was kneaded with a two-roll mill to prepare a curable silicone rubber composition.
  • the obtained curable silicone rubber composition was dispensed to a thickness of 0.25 mm using a calendar molding machine, and then transferred onto a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m.
  • PET polyethylene terephthalate
  • Example 7 A single-layer PTFE film having a thickness of 130 ⁇ m: Nitoflon film (trade name, manufactured by Nitto Denko Corporation, melting point 327 ° C., thermal conductivity 0.2 W / mK) was used.
  • Example 8 PTFE film reinforced with a 45 ⁇ m thick glass cloth: Nitoflon-impregnated glass cloth (trade name, manufactured by Nitto Denko Corporation, melting point 327 ° C., thermal conductivity 0.3 W / mK) was used.
  • Example 9 Polyimide film having a thickness of 50 ⁇ m: Kapton 200H (trade name, manufactured by Toray DuPont Co., Ltd., melting point, no glass transition temperature, thermal conductivity 0.2 W / mK) was used.
  • Kapton 200H trade name, manufactured by Toray DuPont Co., Ltd., melting point, no glass transition temperature, thermal conductivity 0.2 W / mK
  • Example 10 The PTFE film reinforced with a 45 ⁇ m thick glass cloth of Example 8 was used in place of the PET film, and the silicone rubber layer having the composition of Example 1 was heat-cured on the surface of the PTFE film reinforced with the plasma-treated glass cloth.
  • a composite sheet having a two-layer structure in which a PTFE film reinforced with a glass cloth having a total sheet thickness of 0.25 mm and a silicone rubber layer were laminated was prepared.
  • the connection experiment was conducted with the PTFE film side surface reinforced with glass cloth as the solar cell side.
  • Example 11 The layer having the composition of Example 1 was formed to a thickness of 0.25 mm, and the layer having the composition of Example 6 was laminated to a thickness of 0.1 mm so that the total thickness of the sheet was 0.35 mm. A sheet was produced. A connection experiment was conducted with the layer side of the composition of Example 6 as the solar cell side.
  • a 2 mm wide silver-based bus bar current collecting electrode is provided as a front electrode and a back electrode for connecting a wiring member, and a 150 mm wide x 150 mm thick silicon polycrystalline solar cell is prepared.
  • wiring members a strip-shaped copper foil wire having a rectangular cross section with a width of 2 mm and a thickness of 160 ⁇ m, and a strip-shaped solder-plated copper foil wire solder-plated on the copper foil wire were prepared.
  • a composition in which an epoxy insulating adhesive was mixed with nickel particles plated with gold on the surface having an average particle diameter of 6 ⁇ m and formed into a film shape having a width of 2 mm and a thickness of 45 ⁇ m was prepared.
  • sheets of Examples 1 to 11 and Comparative Examples 2 and 3 shown in Table 2 were prepared as connecting sheets for solar cell electrodes, and the front and back electrodes of the silicon polycrystalline solar cell and the wiring member were prepared. Connected. Further, as Comparative Example 1, connection was performed without using a sheet.
  • a wiring member connecting device capable of simultaneously connecting both the front surface electrode and the back surface electrode is used, and the conductive adhesive material is used between the electrode 2 on the silicon substrate 1 and the wiring member 4 as shown in FIG.
  • An electrode connecting sheet 5 was placed on the wiring member with a certain film 3 interposed therebetween, and the device was pressure-bonded by the heating and pressure member 6 of the apparatus.
  • the pressure bonding conditions were set to 10 MPa at 3 MPa by adjusting the set temperature of the heating and pressure member so that the conductive adhesive material was 190 ° C. At this time, the surface temperature of the heating and pressing member exceeded 300 ° C. even when any sheet was used or when no sheet was used.
  • connection experiment results (1) Evaluation of uniformity of connecting portion Total length of solar battery cell: A cross section of all connecting portions having a length of 150 mm was observed with a microscope to evaluate whether there was a uniform and defective portion. A solder plated copper foil wire was used. (2) Passing rate of connection resistance For one type of sheet, the wiring member is connected to the electrodes of 100 solar cells, and whether or not the connection resistance between each electrode and the wiring member is at a usable level. Confirmed and evaluated the pass rate. Copper foil wire was used. (3) Probability of cell cracking For one type of sheet, wiring members were connected to the electrodes of 100 solar cells, and the probability of cell cracking was evaluated. Copper foil wire was used.
  • Non-adhesiveness 1 Copper foil wire non-adhesiveness as a wiring member 2: Solder-plated copper foil wire non-adhesiveness as a wiring member 3: Silver-based bus bar collector electrode non-adhesiveness on the cell surface 4: Epoxy insulating adhesive Conductive adhesive film in which gold-plated nickel particles are blended on the surface with an average particle size of 6 ⁇ m (6) Surface condition evaluation of solar cell electrode connection sheet The same part of one type of sheet is used repeatedly and 10 The wiring member was connected to the electrodes of the single solar battery cell. The state of the sheet such as surface scratches and gloss was visually observed and evaluated. Copper foil wire was used.
  • the solar cell electrode connection sheet of Examples 1 to 11 of the present invention By using the solar cell electrode connection sheet of Examples 1 to 11 of the present invention, by connecting the solar cell electrode and the wiring member by heating and pressurizing via a conductive adhesive material, it can be seen that since the entire surface of the heated / pressurized part can be pressure-bonded at a uniform temperature and pressure, there is no contact failure, reliable connection is possible, and the occurrence of cell cracking can be suppressed. In particular, the optimized silicone rubber sheet or the laminate thereof showed little durability and good durability.

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Abstract

Disclosed is a connection sheet for a solar battery cell electrode, which is a polymer sheet for use in the connection between an electrode for extracting an electric power from a solar battery cell and a wiring member through an electrically conductive adhesive material by heating and pressurizing, and which is intercalated between a heating/pressurizing member and the wiring member upon use.

Description

太陽電池セル電極の接続用シート、太陽電池モジュールの製造方法及び太陽電池モジュールSolar cell electrode connection sheet, solar cell module manufacturing method, and solar cell module
　本発明は、太陽電池セル電極の接続用シート及びこれを用いた太陽電池モジュールの製造方法に関し、更に詳述すると、太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着材料、特に、導電性樹脂接着剤を介して加熱及び加圧して接続するときに使用され、耐熱性が良好であり、高温下で圧着が行われても劣化が小さく、機械的な応力に対しても耐久性が良好なポリマーシートである太陽電池セル電極の接続用シート、該シートを使用した太陽電池モジュールの製造方法に関するものであり、更には、これにより得られた、反りや割れの問題のない太陽電池モジュールに関するものである。 The present invention relates to a solar cell electrode connection sheet and a method of manufacturing a solar cell module using the same, and more specifically, an electrode for taking out electric power of a solar cell and a wiring member are made of a conductive adhesive material, In particular, it is used when connecting by heating and pressurizing via a conductive resin adhesive, has good heat resistance, little degradation even when crimped at high temperatures, and against mechanical stress The present invention relates to a sheet for connecting solar cell electrodes, which is a polymer sheet having good durability, and a method for producing a solar cell module using the sheet, and further, there is no problem of warping or cracking obtained thereby. The present invention relates to a solar cell module.
　太陽電池セルには、その電力を取り出すために、太陽電池セルの電極に導電性の配線部材が接続されている。配線部材としては、多くの場合、平角状の銅箔表面にはんだコートしたものが使用され、太陽電池セルの電極と配線部材は、はんだにより接続されている（特許文献１，２：特開２００４－２０４２５６号，同２００５－５０７８０号公報）。このようなはんだ接続には、比較的高温が必要となり、発電を担う半導体構造部や、電極部とはんだ、電極部材の熱収縮率の違いにより接続部に応力がかかるため、太陽電池セルの反りや割れの原因になっている。 In order to take out the electric power of the solar cell, a conductive wiring member is connected to the electrode of the solar cell. In many cases, a wiring member having a flat copper foil surface coated with solder is used, and the electrode of the solar battery cell and the wiring member are connected by solder (Patent Documents 1 and 2: Japanese Patent Laid-Open No. 2004-2005). -204256, 2005-50780). Such solder connection requires a relatively high temperature, and stress is applied to the connection part due to the difference in the thermal contraction rate of the semiconductor structure part that is responsible for power generation, the electrode part and the solder, and the electrode member. Or cause cracks.
　この対策として、はんだ接続において、応力を緩和する技術が種々提案されている（特許文献３～６：特開２００６－５４３５５号，同２００５－１９１２００号，同２００５－３０２９０２号公報，特開昭６１－２８４９７３号公報）。しかしながら、上記の対策では十分ではないため、はんだの代わりに絶縁性樹脂と導電性粒子を含む導電性樹脂接着剤を用いることが提案されている（特許文献７～１１：特開２００５－１０１５１９号，同２００７－１５８３０２号，同２００７－２１４５３３号，同２００８－２９４３８３号，同２００８－３００４０３号公報）。 As countermeasures against this, various techniques for relieving stress in solder connection have been proposed (Patent Documents 3 to 6: JP-A-2006-54355, JP-A-2005-191200, JP-A-2005-302902, JP-A-61). -284974). However, since the above measures are not sufficient, it has been proposed to use a conductive resin adhesive containing an insulating resin and conductive particles instead of solder (Patent Documents 7 to 11: JP-A-2005-101519). 2007-158302, 2007-214533, 2008-294383, 2008-300403).
　この絶縁性樹脂と導電性粒子を含む導電性樹脂接着剤により、太陽電池セルの電極と配線部材を接続するためには、加熱及び圧着工程が必要となる。
　絶縁性樹脂と導電性粒子を含む異方性導電性接着剤を用いて、加熱・加圧して微細なリード電極同士の接続を行う技術は、液晶ディスプレイを中心として広く実用化されている。このとき、加熱・加圧部材と被圧着部材との間に用いられる熱圧着用シリコーンゴムシートは良く知られている。（特許文献１２～１４：特開平５－１９８３４４号，同６－３６８５３号，同６－２８９３５２号公報） In order to connect the electrode of the solar battery cell and the wiring member with the conductive resin adhesive containing the insulating resin and conductive particles, heating and pressure bonding processes are required.
A technique for connecting fine lead electrodes by heating and pressurizing using an anisotropic conductive adhesive containing an insulating resin and conductive particles has been widely put into practical use mainly for liquid crystal displays. At this time, a silicone rubber sheet for thermocompression bonding used between the heating / pressurizing member and the member to be bonded is well known. (Patent Documents 12 to 14: JP-A-5-198344, JP-A-6-36853, JP-A-6-289352)
　また、シリコーンゴムに、水分を除いた揮発分が０．５％以下であるカーボンブラックを配合して耐熱性を改良したもの（特許文献１５：特開平７－１１０１０号公報）や、ＢＥＴ比表面積が１００ｍ2／ｇ以上のカーボンブラックを配合することによって、耐熱性を更に改良した熱圧着用シリコーンゴムシート（特許文献１６：特開２００３－２６１７６９号公報）や、フッ素系材料積層シート（特許文献１７：特許第３１６９５０１号公報）などが提案されている。 Further, a silicone rubber compounded with carbon black having a volatile content of 0.5% or less excluding moisture to improve heat resistance (Patent Document 15: Japanese Patent Laid-Open No. 7-11010), BET specific surface area Silicone rubber sheet for thermocompression bonding (Patent Document 16: Japanese Patent Application Laid-Open No. 2003-261769) or a fluorine-based material laminated sheet (Patent Document) that has further improved heat resistance by blending carbon black having a mass of 100 m 2 / g or more. 17: Japanese Patent No. 3169501).
　しかし、太陽電池セルの電力を取り出すための電極と配線部材とを、絶縁性樹脂及び導電性粒子を含む導電性接着剤により、加熱及び加圧接続するときに、加熱及び加圧部材と配線部材との間にポリマーからなるシートを介在させることは、提案も検討もされて来なかった。したがって、そのシートの材質や構造についても検討されていない。なお、金属ケイ素粉末を配合したシリコーンゴムとして、特許文献１８～２２（特開平３－１４８７３号公報，特開２０００－６３６７０号，同２００７－１３８１００号，同２００７－１７１９４６号，同２００７－３１１６２８号公報）が知られているが、これらはいずれも太陽電池セルの電極と配線部材の接続工程で使用するシリコーンゴムシートへの応用を考慮しておらず、太陽電池セルの反り、割れ問題を解決するための最適化はなされていなかった。 However, when the electrode and the wiring member for taking out the electric power of the solar battery cell are heated and pressurized and connected by the conductive adhesive containing the insulating resin and the conductive particles, the heating and pressing member and the wiring member are used. There has been no proposal or examination of interposing a polymer sheet between the two. Therefore, the material and structure of the sheet have not been studied. As silicone rubbers containing metal silicon powder, Patent Documents 18 to 22 (Japanese Patent Laid-Open Nos. 3-14873, 2000-63670, 2007-138100, 2007-171946, 2007-31628). However, these do not consider application to the silicone rubber sheet used in the connection process between the solar cell electrodes and wiring members, and solve the problem of warping and cracking of the solar cells. There was no optimization to do that.
特開２００４－２０４２５６号公報JP 2004-204256 A 特開２００５－５０７８０号公報Japanese Patent Laid-Open No. 2005-50780 特開２００６－５４３５５号公報JP 2006-54355 A 特開２００５－１９１２００号公報JP-A-2005-191200 特開２００５－３０２９０２号公報JP 2005-302902 A 特開昭６１－２８４９７３号公報JP-A 61-284773 特開２００５－１０１５１９号公報JP 2005-101519 A 特開２００７－１５８３０２号公報JP 2007-158302 A 特開２００７－２１４５３３号公報JP 2007-214533 A 特開２００８－２９４３８３号公報JP 2008-294383 A 特開２００８－３００４０３号公報JP 2008-300403 A 特開平５－１９８３４４号公報JP-A-5-198334 特開平６－３６８５３号公報JP-A-6-36853 特開平６－２８９３５２号公報JP-A-6-289352 特開平７－１１０１０号公報JP 7-11010 A 特開２００３－２６１７６９号公報JP 2003-261769 A 特許第３１６９５０１号公報Japanese Patent No. 3169501 特開平３－１４８７３号公報JP-A-3-14873 特開２０００－６３６７０号公報JP 2000-63670 A 特開２００７－１３８１００号公報JP 2007-138100 A 特開２００７－１７１９４６号公報JP 2007-171946 A 特開２００７－３１１６２８号公報JP 2007-31628 A
　本発明は、上記事情に鑑みなされたもので、太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着剤を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と配線部材との間に介在させて用いられ、高い耐熱性及び耐久性を有し、はんだや配線部材の金属などと貼り付くことなく、歩留まり良く、高品質な太陽電池及び太陽電池モジュールの製造が可能となる太陽電池セル電極の接続用シート、この接続用シートを用いた太陽電池モジュールの製造方法及びこれによって得られる太陽電池モジュールを提供することを目的とする。 The present invention has been made in view of the above circumstances, and when connecting the electrode and the wiring member for taking out the electric power of the solar battery cell by heating and pressurizing via the conductive adhesive, the heating and pressurizing member, It is used by interposing between wiring members, has high heat resistance and durability, and does not stick to solder or metal of wiring members, etc., and can produce high quality solar cells and solar cell modules. It is an object of the present invention to provide a solar cell electrode connection sheet that is made possible, a method for manufacturing a solar battery module using the connection sheet, and a solar battery module obtained thereby.
　本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、太陽電池セルの電極と配線部材とを導電性接着剤、特に導電性樹脂接着剤を介して加熱・加圧して接続するに際し、加熱・加圧部材と配線部材との間に、好ましくは耐熱性樹脂、フッ素ゴム及びシリコーンゴムから選ばれる１種以上を含むポリマーシートを介在させることが、太陽電池セルの薄膜化による反りや割れの対策として有用であることを見出した。さらには、このポリマーシートの硬さ、弾力性、熱伝導性、非着性の最適化が極めて重要であることがわかった。即ち、熱伝導性を上げるためには、熱伝導性充填剤を配合することが好適であり、金属ケイ素粉末や結晶性二酸化ケイ素粉末を使用した場合には、ポリマーシートの圧縮永久歪を小さくすることが可能となるため、圧着に基づく永久変形による劣化を小さくできることがわかった。したがって、最適化されたポリマーシートである太陽電池セル電極の接続用シートを使用することで、単一セルからなる太陽電池や太陽電池モジュールの製造工程において、接点不良による発電効率の低下を起こすことなく、良好に導電性接着材料を加熱・加圧接着することが容易にでき、配線部材や導電性接着剤等に貼り付くことなく、シートの同一箇所を繰り返して使用して、接続可能であることを見出し、本発明をなすに至った。 As a result of intensive studies in order to achieve the above object, the present inventors have connected the solar cell electrode and the wiring member by heating and pressurizing via a conductive adhesive, particularly a conductive resin adhesive. In doing so, it is possible to interpose a polymer sheet containing at least one selected from a heat-resistant resin, fluororubber and silicone rubber between the heating / pressurizing member and the wiring member. It was found to be useful as a countermeasure against warpage and cracking. Furthermore, it was found that optimization of the hardness, elasticity, thermal conductivity, and non-sticking property of this polymer sheet is extremely important. That is, in order to increase the thermal conductivity, it is preferable to add a thermal conductive filler. When metal silicon powder or crystalline silicon dioxide powder is used, the compression set of the polymer sheet is reduced. Therefore, it was found that deterioration due to permanent deformation based on pressure bonding can be reduced. Therefore, by using the solar cell electrode connection sheet, which is an optimized polymer sheet, in the manufacturing process of solar cells and solar cell modules consisting of a single cell, the power generation efficiency is reduced due to poor contact. It is easy to heat and pressure bond the conductive adhesive material satisfactorily, and can be connected by repeatedly using the same part of the sheet without sticking to the wiring member or conductive adhesive etc. As a result, the inventors have made the present invention.
　即ち、本発明は、下記太陽電池セル電極の接続用シート、太陽電池モジュールの製造方法及び太陽電池モジュールを提供する。
〔請求項１〕
　太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に介在させて使用するポリマーシートであることを特徴とする太陽電池セル電極の接続用シート。
〔請求項２〕
　前記ポリマーシートが、耐熱性樹脂、フッ素ゴム及びシリコーンゴムから選択される１種以上を含む請求項１記載の太陽電池セル電極の接続用シート。
〔請求項３〕
　前記耐熱性樹脂が、ガラス転移温度が２００℃以上又は融点が３００℃以上であるフッ素樹脂及びポリアミド系樹脂から選択される１種以上である請求項２記載の太陽電池セル電極の接続用シート。
〔請求項４〕
　前記ポリマーシートが、無機物及び／又は耐熱性樹脂からなるクロス及び／又は繊維で補強されてなる請求項１～３のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項５〕
　前記ポリマーシートが、金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び炭素の同素体から選択される１種以上の無機物からなる熱伝導性充填剤を含有する請求項１～４のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項６〕
　前記ポリマーシートが、
（Ａ）平均重合度が１００以上である架橋性オルガノポリシロキサン：１００質量部、
（Ｂ）金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び炭素の同素体から選択される少なくとも１種の熱伝導性粉末：０～６００質量部、
（Ｃ）カーボンブラック粉末：０～８０質量部、
（Ｄ）ＢＥＴ比表面積が５０ｍ2／ｇ以上である補強性シリカ粉末：０～５０質量部
及び、
（Ｅ）硬化剤：硬化有効量
を含むシリコーンゴム組成物をシート状に成形して加熱硬化させてなるシリコーンゴムシートである請求項１～５のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項７〕
　（Ｂ）成分である熱伝導性粉末が、５質量部以上配合され、平均粒径１～５０μｍの金属ケイ素粉末である請求項６記載の太陽電池セル電極の接続用シート。
〔請求項８〕
　上記金属ケイ素粉末が、表面に強制酸化膜が形成されてなる請求項７記載の太陽電池セル電極の接続用シート。
〔請求項９〕
　（Ｂ）成分である熱伝導性粉末が、５質量部以上配合され、平均粒径１～５０μｍの結晶性二酸化ケイ素粉末である請求項６記載の太陽電池セル電極の接続用シート。
〔請求項１０〕
　前記シリコーンゴムシートの２３℃における切断時伸びが４０～１，０００％、タイプＡデュロメーターでの硬さが１０～９０である請求項６～９のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１１〕
　熱伝導率が０．３Ｗ／ｍＫ以上である請求項１～１０のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１２〕
　請求項２～１１のいずれか１項記載のポリマーシートから選択される２種以上のシートを積層させてなる請求項１記載の太陽電池セル電極の接続用シート。
〔請求項１３〕
　厚さが０．０１～１ｍｍである請求項１～１２のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１４〕
　前記配線部材が、帯状の導電性部材である請求項１～１３のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１５〕
　前記配線部材が、Ｃｕ，Ａｇ，Ａｕ，Ｆｅ，Ｎｉ，Ｚｎ，Ｃｏ，Ｔｉ，Ｐｂ及びＭｇからなる群より選択される１種以上の金属元素を含む請求項１～１４のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１６〕
　前記配線部材が、はんだで被覆されてなる請求項１～１５のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１７〕
　前記導電性接着材料が、絶縁性樹脂及び導電性粒子を含有する導電性樹脂接着剤である請求項１～１６のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１８〕
　前記導電性接着材料が、フィルム状である請求項１～１７のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項１９〕
　前記導電性接着材料が、はんだである請求項１～１６のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項２０〕
　前記導電性接着材料が、配線部材上に形成されてなる請求項１～１９のいずれか１項記載の太陽電池セル電極の接続用シート。
〔請求項２１〕
　太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に請求項１～２０のいずれか１項記載の接続用シートを介在させて加熱及び加圧することを特徴とする太陽電池モジュールの製造方法。
〔請求項２２〕
　太陽電池セル表面に設けられた電力を取り出すための表面電極及び裏面電極と配線部材とをそれぞれ導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に請求項１～２０のいずれか１項記載の接続用シートを介在させて、上記表面電極及び裏面電極と上記配線部材とをそれぞれ同時に加熱及び加圧して接続する請求項２１記載の太陽電池モジュールの製造方法。
〔請求項２３〕
　太陽電池セルの電力を取り出すための電極と配線部材が接続された単一の太陽電池セルで構成される太陽電池モジュールであって、請求項２１又は２２記載の製造方法によって得られることを特徴とする太陽電池モジュール。
〔請求項２４〕
　請求項２３記載の太陽電池セルが複数配列され、互いに隣接する前記太陽電池セルの電力を取り出すための電極が配線部材により接続されていることを特徴とする太陽電池モジュール。 That is, the present invention provides the following solar cell electrode connection sheet, solar cell module manufacturing method, and solar cell module.
[Claim 1]
Polymer used by interposing between the heating and pressure member and the wiring member when connecting the electrode and wiring member for taking out the electric power of the solar cell by heating and pressing the conductive adhesive material. A sheet for connecting solar cell electrodes, characterized by being a sheet.
[Claim 2]
The solar cell electrode electrode connection sheet according to claim 1, wherein the polymer sheet contains one or more selected from a heat-resistant resin, fluororubber and silicone rubber.
[Claim 3]
The solar cell connection sheet according to claim 2, wherein the heat-resistant resin is at least one selected from a fluororesin and a polyamide-based resin having a glass transition temperature of 200 ° C or higher or a melting point of 300 ° C or higher.
[Claim 4]
The solar cell electrode connection sheet according to any one of claims 1 to 3, wherein the polymer sheet is reinforced with a cloth and / or fiber made of an inorganic material and / or a heat resistant resin.
[Claim 5]
The polymer sheet contains a thermally conductive filler made of one or more inorganic substances selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon allotropes. The sheet | seat for connection of the photovoltaic cell electrode of any one of these.
[Claim 6]
The polymer sheet is
(A) Crosslinkable organopolysiloxane having an average degree of polymerization of 100 or more: 100 parts by mass,
(B) at least one heat conductive powder selected from metal, metal oxide, metal nitride, metal carbide, metal hydroxide and carbon allotrope: 0 to 600 parts by mass;
(C) Carbon black powder: 0 to 80 parts by mass,
(D) Reinforcing silica powder having a BET specific surface area of 50 m 2 / g or more: 0 to 50 parts by mass;
The solar cell electrode connection according to any one of claims 1 to 5, wherein (E) a curing agent is a silicone rubber sheet obtained by forming a silicone rubber composition containing an effective amount of curing into a sheet and curing it by heating. Sheet.
[Claim 7]
The solar cell electrode connection sheet according to claim 6, wherein the thermal conductive powder as the component (B) is a metal silicon powder having an average particle diameter of 1 to 50 µm blended in an amount of 5 parts by mass or more.
[Claim 8]
The solar cell electrode connection sheet according to claim 7, wherein the metal silicon powder has a forced oxide film formed on a surface thereof.
[Claim 9]
The solar cell electrode connection sheet according to claim 6, wherein the thermal conductive powder as component (B) is a crystalline silicon dioxide powder blended in an amount of 5 parts by mass or more and having an average particle size of 1 to 50 µm.
[Claim 10]
The solar cell electrode connection according to any one of claims 6 to 9, wherein the silicone rubber sheet has an elongation at break at 23 ° C of 40 to 1,000% and a hardness with a type A durometer of 10 to 90. Sheet.
[Claim 11]
The solar cell electrode connecting sheet according to any one of claims 1 to 10, which has a thermal conductivity of 0.3 W / mK or more.
[Claim 12]
The solar cell electrode connection sheet according to claim 1, wherein two or more kinds of sheets selected from the polymer sheets according to any one of claims 2 to 11 are laminated.
[Claim 13]
The solar cell electrode connection sheet according to any one of claims 1 to 12, which has a thickness of 0.01 to 1 mm.
[Claim 14]
The solar cell electrode connection sheet according to any one of claims 1 to 13, wherein the wiring member is a strip-shaped conductive member.
[Claim 15]
15. The wiring member according to claim 1, wherein the wiring member includes one or more metal elements selected from the group consisting of Cu, Ag, Au, Fe, Ni, Zn, Co, Ti, Pb, and Mg. Sheet for connecting solar cell electrodes.
[Claim 16]
The solar cell electrode connection sheet according to any one of claims 1 to 15, wherein the wiring member is coated with solder.
[Claim 17]
The connection sheet for solar cell electrodes according to any one of claims 1 to 16, wherein the conductive adhesive material is a conductive resin adhesive containing an insulating resin and conductive particles.
[Claim 18]
The connection sheet for solar cell electrodes according to any one of claims 1 to 17, wherein the conductive adhesive material is in a film form.
[Claim 19]
The solar cell electrode connection sheet according to any one of claims 1 to 16, wherein the conductive adhesive material is solder.
[Claim 20]
The solar cell electrode connection sheet according to any one of claims 1 to 19, wherein the conductive adhesive material is formed on a wiring member.
[Claim 21]
The electrode for taking out the electric power of the solar battery cell and the wiring member are connected by heating and pressing the conductive adhesive material between the heating and pressing member and the wiring member. A method for manufacturing a solar cell module, comprising heating and pressurizing the sheet for connection according to any one of the preceding claims.
[Claim 22]
When connecting the surface electrode and the back electrode for taking out electric power provided on the surface of the solar battery cell and the wiring member by heating and pressing through the conductive adhesive material, respectively, the heating and pressing member and the wiring member The solar cell according to claim 21, wherein the connection sheet according to any one of claims 1 to 20 is interposed between the front surface electrode, the back surface electrode, and the wiring member by simultaneously heating and pressurizing the solar cell. Manufacturing method of battery module.
[Claim 23]
It is a solar cell module comprised by the single solar cell to which the electrode and wiring member for taking out the electric power of a photovoltaic cell were connected, Comprising: It is obtained by the manufacturing method of Claim 21 or 22 characterized by the above-mentioned. Solar cell module.
[Claim 24]
24. A solar cell module, wherein a plurality of solar cells according to claim 23 are arranged, and electrodes for taking out electric power of the solar cells adjacent to each other are connected by a wiring member.
　本発明によれば、太陽電池セルの電力を取り出すための電極と配線部材とを、導電性接着材料を介して加熱及び加圧して接続するに際し、ポリマーシートからなる最適化された太陽電池セル電極の接続用シートを加熱及び加圧部材と配線部材との間に介在させて使用することから、被加熱・加圧部全面を均一な温度及び圧力で圧着できる。その結果、接点不良がなく、確実な接続が可能となり、高品質で長期耐久性も良好な単一の太陽電池セルからなる太陽電池と、複数の太陽電池セルが配列して接続した構造の太陽電池モジュールを安定的に製造し、市場に供給することができる。 According to the present invention, an optimized solar cell electrode made of a polymer sheet is used to connect an electrode for taking out electric power of a solar cell and a wiring member by heating and pressurizing via a conductive adhesive material. Since the connecting sheet is interposed between the heating and pressure member and the wiring member, the entire surface of the heated / pressurized part can be pressure-bonded at a uniform temperature and pressure. As a result, there is no contact failure, a reliable connection is possible, a solar cell consisting of a single solar cell with high quality and good long-term durability, and a solar cell with a structure in which a plurality of solar cells are arranged and connected Battery modules can be manufactured stably and supplied to the market.
　特に、導電性接着材料として、絶縁性樹脂と導電性粒子を含有した導電性樹脂接着剤を使用する場合には、太陽電池セルの反りや割れの問題を解消した太陽電池セルと太陽電池モジュールを安定的に製造し、市場に供給することができる。今後、太陽電池セルの薄膜化が進むと予測されており、さらに大きな効果が期待できる。
　本発明の太陽電池セル電極の接続用シートは、圧着時にはみ出した導電性接着材料と加熱及び加圧部材との貼り付きを防止したり、導電性接着材料が加熱及び加圧部材上に堆積することを防止したりする効果もある。加熱及び加圧部材は、通常、金属製の硬いものであるため、接続用シートは、圧着時の加熱及び加圧部材からの衝撃を和らげ、太陽電池セルの割れを防ぐ役割も担う。
　また、本発明の太陽電池セル電極の接続用シートは、圧着時に接触する配線部材、導電性接着材料、表面電極などの部材に非接着性を有することで、シートの同一箇所を使用して、繰り返して圧着が可能となり、コスト削減及び省力化された信頼性のある接続が可能となる。 In particular, when a conductive resin adhesive containing an insulating resin and conductive particles is used as the conductive adhesive material, the solar battery cell and the solar battery module that have solved the problem of warping and cracking of the solar battery cell It can be manufactured stably and supplied to the market. In the future, it is predicted that the thinning of solar cells will progress, and a greater effect can be expected.
The sheet for connecting solar cell electrodes according to the present invention prevents sticking between the conductive adhesive material and the heating and pressing member that protrudes during pressure bonding, or the conductive adhesive material is deposited on the heating and pressing member. There is also an effect to prevent this. Since the heating and pressurizing members are usually hard metal, the connecting sheet also plays a role of mitigating the impact from the heating and pressurizing members at the time of pressure bonding and preventing cracking of the solar cells.
In addition, the sheet for connecting solar cell electrodes of the present invention has a non-adhesive property to members such as a wiring member, a conductive adhesive material, and a surface electrode that are in contact with each other at the time of crimping. Repetitive crimping is possible, and a reliable connection with reduced cost and labor saving is possible.
本発明の実施例において用いた太陽電池セル及び接続用シートの断面図である。It is sectional drawing of the photovoltaic cell and the sheet | seat for connection which were used in the Example of this invention. 太陽電池セル接続の一例を示す。ａは平面図であり、ｂは断面図であり、ｃは太陽電池セルの断面拡大図である。An example of a photovoltaic cell connection is shown. a is a plan view, b is a cross-sectional view, and c is an enlarged cross-sectional view of a solar battery cell.
　本発明の電極接続用シートは、太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に介在させて使用され、好ましくは耐熱性樹脂、フッ素ゴム及びシリコーンゴムから選択される１種以上を含むポリマーシートであることを特徴とする。 The electrode connecting sheet of the present invention, when connecting the electrode for taking out the power of the solar battery cell and the wiring member by heating and pressing through the conductive adhesive material, the heating and pressing member and the wiring member The polymer sheet is preferably a polymer sheet containing at least one selected from a heat-resistant resin, fluororubber and silicone rubber.
太陽電池の種類
　本発明の太陽電池セル電極の接続用シートが使用される太陽電池セルの種類としては、電力を取り出すための電極が備えられたものであれば特に限定されるものではないが、その太陽光を光電変換して電力を発生させる材料により、シリコン系、化合物系、有機系などを挙げることができる。例えば、シリコン系の場合には、単結晶シリコン型、多結晶シリコン型、微結晶シリコン型、アモルファスシリコン型、結晶シリコンとアモルファスシリコンのハイブリッド型（ＨＩＴ型）などを挙げることができる。化合物系の場合には、ＧａＡｓ単結晶などのＩＩＩ－Ｖ族系のもの、ＣＩＳ系（カルコパライト系）と呼ばれるＩ－ＩＩＩ－Ｖ族化合物からなるもの、例えば、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ2、Ｃｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）2、ＣｕＩｎＳ2などで、それぞれＣＩＧＳ、ＣＩＧＳＳ、ＣＩＳと呼ばれるもの、ＣｄＴｅ－ＣｄＳ系などが挙げられる。有機系の場合には、色素増感型、有機薄膜型などが挙げられる。また、その厚さによる分類では、比較的厚い結晶系の太陽電池と、ガラス上やフィルム上に薄く製膜した薄膜太陽電池を挙げることができる。 Type of solar cell The type of solar cell in which the solar cell electrode connection sheet of the present invention is used is not particularly limited as long as an electrode for taking out electric power is provided, Examples of the material that photoelectrically converts the sunlight to generate electric power include silicon-based, compound-based, and organic-based materials. For example, in the case of silicon, a single crystal silicon type, a polycrystalline silicon type, a microcrystalline silicon type, an amorphous silicon type, a hybrid type of crystalline silicon and amorphous silicon (HIT type), and the like can be given. In the case of a compound system, a group III-V group such as a GaAs single crystal, a group consisting of a group I-III-V compound called a CIS system (calcopalite system), for example, Cu (In, Ga) Se 2 , Cu (In, Ga) (Se, S) 2 , CuInS 2, etc., which are called CIGS, CIGSS, CIS, CdTe—CdS system, etc., respectively. In the case of an organic system, a dye-sensitized type, an organic thin film type, and the like are exemplified. Moreover, according to the classification according to the thickness, a relatively thick crystalline solar cell and a thin film solar cell thinly formed on glass or a film can be exemplified.
圧着系
　太陽電池セルの電力を取り出すための電極の形状としては、例えば、フィンガー、バスバーと呼ばれる集電電極を、銀などを主成分として形成してあっても良いし、特に集電電極を設けていない構造であっても良く、これらに限定されるものではない。
　配線部材は、例えば、断面が平角形状を有する帯状の導電性部材であることが好ましく、材質としては、Ｃｕ，Ａｇ，Ａｕ，Ｆｅ，Ｎｉ，Ｚｎ，Ｃｏ，Ｔｉ，Ｐｂ及びＭｇからなる群より選択される１種以上の金属元素を含むものが好ましい。
　さらに、必要に応じて、配線部材が、はんだで被覆されたものを使用しても良い。 As the shape of the electrode for taking out the electric power of the crimping solar cell, for example, a collecting electrode called a finger or a bus bar may be formed with silver as a main component, and in particular, a collecting electrode is provided. However, the structure may not be limited to these.
For example, the wiring member is preferably a strip-shaped conductive member having a flat cross section, and the material is selected from the group consisting of Cu, Ag, Au, Fe, Ni, Zn, Co, Ti, Pb and Mg. Those containing one or more selected metal elements are preferred.
Furthermore, if necessary, the wiring member covered with solder may be used.
　導電性接着材料は、絶縁性樹脂と導電性粒子とを含有する導電性樹脂接着剤が好適であり、ペースト状で使用することもできるが、フィルム状に成形したものを使用することで、製造工程を簡略化できるため好適である。さらに、予め配線部材上に形成したものも使用することもできる。導電性接着材料に用いる絶縁性樹脂は、エポキシ系、アクリル系、フェノキシ系、ポリイミド系、シリコーン系、ウレタン系やそれらを変性したものなどから任意のものを選択することができるし、これらを混合して用いても良く、これらに限定されるものではない。具体的には、熱硬化型のエポキシ樹脂、アクリル樹脂にアクリルゴム又はブチルゴム成分を含有し、動的粘弾性率が１×１０3～１×１０10Ｐａ等の樹脂を挙げることができる。また、必要に応じて、導電性接着材料として、はんだを使用することができる。 As the conductive adhesive material, a conductive resin adhesive containing an insulating resin and conductive particles is suitable, and it can be used in the form of a paste, but it is manufactured by using a film-shaped material. This is preferable because the process can be simplified. Furthermore, what was previously formed on the wiring member can also be used. The insulating resin used for the conductive adhesive material can be selected from an epoxy resin, an acrylic resin, a phenoxy resin, a polyimide resin, a silicone resin, a urethane resin, or a modified one thereof, or a mixture thereof. However, the present invention is not limited to these. Specifically, a thermosetting epoxy resin or an acrylic resin containing an acrylic rubber or butyl rubber component and a dynamic viscoelastic modulus of 1 × 10 3 to 1 × 10 10 Pa can be used. Further, if necessary, solder can be used as the conductive adhesive material.
　上記樹脂接着剤に混合して用いられる導電性粒子としては、Ｃｕ，Ａｇ，Ａｕ，Ｆｅ，Ｎｉ，Ｚｎ，Ｃｏ，Ｔｉ，Ｐｂ，Ｍｇ，はんだ等の粒子、スチレン等の樹脂、ガラスやシリカ粒子表面に前記金属から選ばれる金属をめっき処理した粒子等の金属粒子が挙げられ、これらの粒子の平均粒径は１～１００μｍであることが好ましく、より好ましくは２～８０μｍである。なお、平均粒径はレーザー回折法による粒度分布測定装置を用いて、累積重量平均値Ｄ50（又はメジアン径）などとして求めることができる。 The conductive particles used by mixing with the resin adhesive include Cu, Ag, Au, Fe, Ni, Zn, Co, Ti, Pb, Mg, solder and other particles, styrene and other resins, glass and silica particles. Examples thereof include metal particles such as particles obtained by plating a metal selected from the above metals on the surface, and the average particle size of these particles is preferably 1 to 100 μm, more preferably 2 to 80 μm. The average particle diameter can be obtained as a cumulative weight average value D 50 (or median diameter) or the like using a particle size distribution measuring apparatus by a laser diffraction method.
太陽電池セル電極の接続用シート材質、構成
　本発明の太陽電池セル電極の接続用シートは、絶縁性樹脂と導電性粒子とを含有する導電性樹脂接着材料を加熱硬化させたり、はんだを溶融させたりするために、通常３００℃以上に熱せられた配線部材接続装置の加熱・加圧部材に接触して使用されることが多いため、耐熱性が必要であることから、その材質は、耐熱性の高分子材料であることが好ましい。具体的には、耐熱性樹脂、フッ素ゴム、シリコーンゴムから選択してなる１種以上のポリマーである。さらに、耐熱性樹脂としては、そのガラス転移温度が２００℃以上又は融点が３００℃以上であるフッ素樹脂及びポリアミド系樹脂から選択される１種以上であることが好ましい。耐熱性樹脂のガラス転移温度又は融点の上限値は特に制限されないが、通常、５００℃以下であることが好ましい。 Sheet material for connecting solar cell electrode, composition The sheet for connecting solar cell electrode of the present invention is obtained by heating and curing a conductive resin adhesive material containing an insulating resin and conductive particles or by melting solder. In general, it is used in contact with the heating / pressurizing member of the wiring member connecting apparatus that is usually heated to 300 ° C. or higher. The polymer material is preferably. Specifically, it is at least one polymer selected from a heat-resistant resin, fluororubber, and silicone rubber. Furthermore, the heat resistant resin is preferably at least one selected from fluororesins and polyamide resins having a glass transition temperature of 200 ° C. or higher or a melting point of 300 ° C. or higher. The upper limit value of the glass transition temperature or melting point of the heat resistant resin is not particularly limited, but it is usually preferably 500 ° C. or lower.
　例えば、融点が３００℃以上のフッ素樹脂としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、ポリ３フッ化塩化エチレン（ＰＴＦＣＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等が挙げられるが、これらに限定されるものではない。ガラス転移温度が２００℃以上のポリアミド系樹脂としては、芳香族ポリイミド、ポリアミドイミド、芳香族ポリアミド、ポリエーテルサルホン、ポリエーテルイミド等が例示できるが、これらに限定されるものではない。アラミド繊維に含浸させた耐熱シートなどの樹脂系シートも例示できる。上記から変性される耐熱性のフッ素系ゴムも使用することができる。 For example, fluororesins having a melting point of 300 ° C. or more include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polytrifluoroethylene chloride (PTFCE), polyvinylidene fluoride ( PVDF) and the like, but are not limited thereto. Examples of the polyamide resin having a glass transition temperature of 200 ° C. or higher include aromatic polyimide, polyamideimide, aromatic polyamide, polyethersulfone, and polyetherimide, but are not limited thereto. A resin-based sheet such as a heat-resistant sheet impregnated with aramid fibers can also be exemplified. A heat-resistant fluororubber modified from the above can also be used.
　本発明の太陽電池セル電極の接続用シートは、加熱・加圧部材からの熱を導電性接着部材に伝える必要があるため、ある程度熱伝導率が高いほうが好ましい。高分子材料の熱伝導率は比較的低いことから、高分子材料中に無機物からなる熱伝導性充填剤を添加することで、シートの熱伝導率を高めることが好ましい。無機物からなる熱伝導性充填剤としては、金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物、及び炭素の同素体から選択される１種以上の材料であることが好ましい。金属からなる熱伝導性充填剤としては、金属ケイ素、アルミニウム、金、銀、銅、鉄、ニッケル及びこれらの合金の中から選択される１種以上の金属粉末であることが好ましい。金属酸化物としては、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、二酸化ケイ素、酸化鉄など、金属窒化物としては、窒化ホウ素、窒化アルミニウム、窒化ケイ素など、金属炭化物としては、炭化ケイ素、炭化ホウ素など、金属水酸化物としては、水酸化アルミニウムなど、炭素の同素体としては、各種炭素繊維や黒鉛などを用いることができる。これらの熱伝導性充填剤の配合量は、上記高分子材料１００質量部に対して１０～３０００質量部であることが好ましい。 The solar cell electrode connection sheet of the present invention preferably has a high thermal conductivity to some extent because it is necessary to transfer heat from the heating / pressurizing member to the conductive adhesive member. Since the thermal conductivity of the polymer material is relatively low, it is preferable to increase the thermal conductivity of the sheet by adding a thermally conductive filler made of an inorganic substance into the polymer material. The thermally conductive filler made of an inorganic material is preferably one or more materials selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon allotropes. The heat conductive filler made of metal is preferably one or more metal powders selected from metal silicon, aluminum, gold, silver, copper, iron, nickel, and alloys thereof. Examples of metal oxides include zinc oxide, aluminum oxide, magnesium oxide, silicon dioxide, and iron oxide. Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride. Examples of metal carbides include silicon carbide and boron carbide. Examples of the metal hydroxide include aluminum hydroxide, and examples of the carbon allotrope include various carbon fibers and graphite. The blending amount of these thermally conductive fillers is preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the polymer material.
太陽電池セル電極の接続用シートがシリコーンゴムの場合
　次に、本発明に用いられるシリコーンゴムを形成するためのシリコーンゴム組成物について説明する。
［組成物］
　本発明の太陽電池セル電極の接続用シートに必要な主な特性としては、クッション性、耐熱圧着性、熱伝導性が挙げられる。シリコーンゴムは、特に適度なクッション性を持つよう伸びや硬度を調整することが容易であり、耐熱圧着性も良好であり、熱伝導性充填剤の添加で熱伝導率を高めることができるため、本発明の太陽電池セル電極の接続用シートの材料として好適である。 When the solar cell electrode connecting sheet is made of silicone rubber Next, the silicone rubber composition for forming the silicone rubber used in the present invention will be described.
[Composition]
The main characteristics required for the solar cell electrode connection sheet of the present invention include cushioning properties, heat-resistant pressure bonding properties, and thermal conductivity. Silicone rubber is particularly easy to adjust the elongation and hardness so as to have an appropriate cushioning property, has good heat-resistant pressure-bonding properties, and can add heat conductive filler to increase thermal conductivity. It is suitable as a material for the connection sheet of the solar battery cell electrode of the present invention.
　本発明において使用されるシリコーンゴム組成物としては、例えば、
（Ａ）平均重合度が１００以上であるオルガノポリシロキサン及び
（Ｅ）硬化剤
を含み、必要により
（Ｂ）金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び炭素の同素体から選択される少なくとも１種の熱伝導性粉末、
（Ｃ）カーボンブラック粉末、
（Ｄ）ＢＥＴ比表面積が５０ｍ2／ｇ以上である補強性シリカ粉末
を配合してなるものが挙げられる。 As a silicone rubber composition used in the present invention, for example,
(A) An organopolysiloxane having an average degree of polymerization of 100 or more and (E) a curing agent, and if necessary, from (B) an allotrope of metal, metal oxide, metal nitride, metal carbide, metal hydroxide and carbon At least one thermally conductive powder selected;
(C) carbon black powder,
(D) The thing formed by mix | blending the reinforcing silica powder whose BET specific surface area is 50 m < 2 > / g or more is mentioned.
　本発明に用いられるシリコーンゴム組成物における（Ａ）～（Ｅ）成分について説明する。
（Ａ）成分：
　本発明で使用する（Ａ）成分である、平均重合度１００以上の架橋性オルガノポリシロキサンは、例えば、次の平均組成式（１）で表される。
　ＲnＳｉＯ(4-n)/2・・・・（１）
（但し、（１）式中のｎは１．９～２．４の正数、Ｒは置換又は非置換の一価の炭化水素基を表す。） The components (A) to (E) in the silicone rubber composition used in the present invention will be described.
(A) component:
The crosslinkable organopolysiloxane having an average degree of polymerization of 100 or more, which is the component (A) used in the present invention, is represented by the following average composition formula (1), for example.
R n SiO (4-n) / 2 (1)
(In the formula (1), n represents a positive number of 1.9 to 2.4, and R represents a substituted or unsubstituted monovalent hydrocarbon group.)
　Ｒで表される置換又は非置換の一価炭化水素基の具体例としては、メチル基、エチル基、プロピル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基等のアルケニル基、フェニル基、トリル基等のアリール基、あるいは、これらの基の水素原子の一部又は全部が塩素原子、フッ素原子などのハロゲン原子で置換されたハロゲン化炭化水素基等が例示される。 Specific examples of the substituted or unsubstituted monovalent hydrocarbon group represented by R include alkyl groups such as methyl group, ethyl group and propyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, vinyl group and allyl group. Examples thereof include aryl groups such as alkenyl groups, phenyl groups, tolyl groups, etc., or halogenated hydrocarbon groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine atoms or fluorine atoms. Is done.
　（Ａ）成分のオルガノポリシロキサンとしては、主鎖がジメチルシロキサン単位からなるもの、あるいはこのオルガノポリシロキサンの主鎖にメチル基、ビニル基、フェニル基、トリフルオロプロピル基などの有機基を導入したものが好ましい。特に、前記有機基の０．０００１～１０モル％がビニル基であり、かつ８０モル％以上がメチル基であることが好ましい。また分子鎖末端がトリオルガノシリル基又は水酸基で封鎖されたものが好ましい。このトリオルガノシリル基としては、トリメチルシリル基、ジメチルビニルシリル基、トリビニルシリル基などが例示される。 As the organopolysiloxane of component (A), the main chain is composed of dimethylsiloxane units, or an organic group such as methyl group, vinyl group, phenyl group or trifluoropropyl group is introduced into the main chain of this organopolysiloxane. Those are preferred. In particular, it is preferable that 0.0001 to 10 mol% of the organic group is a vinyl group and 80 mol% or more is a methyl group. Further, those having molecular chain ends blocked with triorganosilyl groups or hydroxyl groups are preferred. Examples of the triorganosilyl group include a trimethylsilyl group, a dimethylvinylsilyl group, and a trivinylsilyl group.
　（Ａ）成分のオルガノポリシロキサンとしては、１種だけを使用しても複数種を混合して使用しても良いが、前記（１）式で表される（Ａ）成分のオルガノポリシロキサン分子全体が有する、全Ｒの０．１０～０．５０モル％がビニル基であることが好ましい。また本発明においては、（１）式で表される（Ａ）成分の平均重合度は１００以上、特に２００以上であることが好ましい。平均重合度が１００未満であると、硬化後の機械的強度が劣る場合がある。平均重合度の上限は特に制限されないが、１００，０００以下、特に５０，０００以下であることが好ましい。なお、平均重合度は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算値である。 The organopolysiloxane of component (A) may be used alone or as a mixture of a plurality of types, but the organopolysiloxane molecule of component (A) represented by the above formula (1) It is preferable that 0.10 to 0.50 mol% of all R in the whole is a vinyl group. Moreover, in this invention, it is preferable that the average degree of polymerization of (A) component represented by (1) Formula is 100 or more, especially 200 or more. If the average degree of polymerization is less than 100, the mechanical strength after curing may be inferior. The upper limit of the average degree of polymerization is not particularly limited, but is preferably 100,000 or less, particularly preferably 50,000 or less. In addition, an average degree of polymerization is a polystyrene conversion value by gel permeation chromatography (GPC).
（Ｂ）成分：
　（Ｂ）成分は、熱伝導性を与えるために添加するもので、高い熱伝導率が必要な場合に用いるものである。これは、金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び炭素の同素体から選択される少なくとも１種の熱伝導性粉末であり、本発明のシリコーンゴムシートに熱伝導性を付与する充填剤である。これらの具体例は、金属としては、金、銀、銅、鉄、金属ケイ素、ニッケル、アルミニウム及びこれらの合金など、金属酸化物としては、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、二酸化ケイ素、酸化鉄など、金属窒化物としては、窒化ホウ素、窒化アルミニウム、窒化ケイ素など、金属炭化物としては、炭化ケイ素、炭化ホウ素など、金属水酸化物としては、水酸化アルミニウムなど、炭素の同素体としては、各種炭素繊維や黒鉛などが例示されるが、これらに限定されるわけではない。 (B) component:
The component (B) is added to give thermal conductivity, and is used when high thermal conductivity is required. This is at least one heat conductive powder selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides and allotropes of carbon, and provides heat conductivity to the silicone rubber sheet of the present invention. It is a filler to be applied. Specific examples of these include gold, silver, copper, iron, metal silicon, nickel, aluminum and alloys thereof as metals, and zinc oxide, aluminum oxide, magnesium oxide, silicon dioxide, iron oxide as metal oxides. Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride; metal carbides such as silicon carbide and boron carbide; metal hydroxides such as aluminum hydroxide; and carbon allotropes such as various carbons. Examples thereof include fibers and graphite, but are not limited thereto.
　上記の熱伝導性粉末の中でも、特に金属ケイ素粉末や結晶性二酸化ケイ素粉末が好適である。これらの粉末を使用することによって、圧縮成形歪を小さくすることが可能となり、繰り返し圧着によって生じる永久変形による劣化が小さくなるので、耐久性に優れた熱圧着用シリコーンゴムシートの実現が可能となる。また、両粉末とも低比重であり、シートの比重を軽くすることができるので、熱圧着用シリコーンゴムシートの取扱い性が良好になる。 Among the above heat conductive powders, metal silicon powder and crystalline silicon dioxide powder are particularly suitable. By using these powders, it becomes possible to reduce the compression molding distortion, and the deterioration due to permanent deformation caused by repeated pressure bonding is reduced, so that it is possible to realize a silicone rubber sheet for thermocompression bonding with excellent durability. . Further, both powders have a low specific gravity, and the specific gravity of the sheet can be reduced, so that the handleability of the silicone rubber sheet for thermocompression bonding is improved.
　これらの粉末の形状は、球状、楕円状、扁平状、角張った不定形、丸みを帯びた不定形、針状などの何れでも良く、特に限定されるものではない。例えば、金属ケイ素の場合には、球状、粉砕による不定形などを例示することができる。 The shape of these powders may be any of spherical, oval, flat, angular irregular shape, round irregular shape, needle shape, etc., and is not particularly limited. For example, in the case of metallic silicon, spherical shapes, irregular shapes by pulverization, and the like can be exemplified.
　また、熱伝導性粉末の純度は、特に限定されるものではないが、熱伝導性を付与する観点から５０質量％以上であることが好ましく、特に８０質量％以上、さらに好ましくは９５質量％以上である。 The purity of the heat conductive powder is not particularly limited, but is preferably 50% by mass or more, particularly 80% by mass or more, more preferably 95% by mass or more from the viewpoint of imparting thermal conductivity. It is.
　ここで、本発明に用いる金属ケイ素粉末の製造方法としては、特に限定されるものではないが、珪石を還元して金属ケイ素としたものをボールミル等既存の破砕機や粉砕器にて粉砕したもの、半導体製造工程等より発生する金属ケイ素（ウエハー）や切削くず等を原料として微粉化したものなど、粉砕法により粉末化したもの、金属ケイ素を高温で溶融したものを気相法で微粒子化し、冷却、固化して球状粒子としたものなどの球形金属ケイ素粉末（ここで“球状”又は“球形”とは、個々の粒子表面に鋭く尖ったエッヂ部分がない、なめらかな形状であることを意味するもので、通常、長径／短径の比率（アスペクト比）が１．０～１．４、好ましくは１．０～１．２程度のものを示す。）等が挙げられ、金属ケイ素の結晶構造の単結晶、多結晶は任意である。微粒子化した金属ケイ素粉末の純度は、特に限定されるものではないが、熱伝導性付与の観点から５０質量％以上（即ち、５０～１００質量％）が好適であり、より好ましくは８０質量％以上（８０～１００質量％）、更に好ましくは９５質量％以上（９５～１００質量％）であることが望ましい。純度の高い金属ケイ素粉末は表面の自然酸化膜に欠陥がなく、高温熱安定性が良好となる。
　また、酸化膜を設けるためには、粉体流動層にて空気流動させながら、１００℃以上の加熱処理を１時間以上行うことが好ましい。 Here, the method for producing the metal silicon powder used in the present invention is not particularly limited, but a product obtained by reducing silica into metal silicon by pulverization with an existing crusher or pulverizer such as a ball mill. , Pulverized metal silicon (wafer) generated from semiconductor manufacturing processes, etc., and powdered by pulverization method, and metal silicon melted at high temperature to be micronized by gas phase method, Spherical metal silicon powders such as those that have been cooled and solidified into spherical particles (here “spherical” or “spherical” means a smooth shape with no sharp edges on the surface of each particle) In general, the ratio of major axis / minor axis (aspect ratio) is 1.0 to 1.4, preferably about 1.0 to 1.2). Single crystal of structure, Crystal is optional. The purity of the finely divided metal silicon powder is not particularly limited, but is preferably 50% by mass or more (ie, 50 to 100% by mass) from the viewpoint of imparting thermal conductivity, and more preferably 80% by mass. It is desirable that the amount is 80% to 100% by mass, more preferably 95% by mass or more (95% to 100% by mass). High-purity metallic silicon powder has no defects in the natural oxide film on the surface and has good high-temperature thermal stability.
In order to provide an oxide film, it is preferable to perform heat treatment at 100 ° C. or higher for 1 hour or longer while air-flowing in the powder fluidized bed.
　本発明に使用する（Ｂ）成分の金属ケイ素粉末や結晶性二酸化ケイ素粉末等の平均粒径は５０μｍ以下であり、好ましくは１～５０μｍ、より好ましくは１～２５μｍ、特に２～２５μｍであるものを使用する。平均粒径が１μｍ未満の粒子は、製造が困難であると共に、多量に配合するのが困難となる場合があり、５０μｍを超えるとゴム硬化物の機械的強度が損なわれる場合があるだけでなく、シートとしての表面性能に問題が生じるおそれがある。 The average particle size of the component (B) metal silicon powder or crystalline silicon dioxide powder used in the present invention is 50 μm or less, preferably 1 to 50 μm, more preferably 1 to 25 μm, especially 2 to 25 μm. Is used. Particles having an average particle size of less than 1 μm are difficult to manufacture and may be difficult to mix in large quantities. If the particle size exceeds 50 μm, the mechanical strength of the rubber cured product may be impaired. There may be a problem in the surface performance of the sheet.
　なお、平均粒径は、レーザー光回折法等による粒度分布測定装置を用いて、累積重量平均値Ｄ50（又はメジアン径）などとして求めることができる。 The average particle diameter can be determined as a cumulative weight average value D 50 (or median diameter) or the like using a particle size distribution measuring apparatus such as a laser light diffraction method.
　また、（Ｂ）成分の金属ケイ素粉末は、シリコーンゴム組成物の熱安定性や粉体の配合性の向上を目的として、シラン系カップリング剤又はその部分加水分解物、アルキルアルコキシシラン又はその部分加水分解物、有機シラザン類、チタネート系カップリング剤、オルガノポリシロキサンオイル、加水分解性官能基含有オルガノポリシロキサン等により表面処理されたものであってもよい。これら処理は、無機粉体自体を予め処理しても、あるいは（Ａ）成分との混合時に処理を行ってもよい。 The component (B) metal silicon powder is a silane coupling agent or a partial hydrolyzate thereof, an alkylalkoxysilane or a part thereof for the purpose of improving the thermal stability of the silicone rubber composition and the compounding property of the powder. It may be surface-treated with a hydrolyzate, an organic silazane, a titanate coupling agent, an organopolysiloxane oil, a hydrolyzable functional group-containing organopolysiloxane, or the like. In these treatments, the inorganic powder itself may be treated in advance, or may be treated at the time of mixing with the component (A).
　本発明における（Ｂ）成分の配合量は、（Ａ）成分１００質量部に対して０～６００質量部で良いが、特に５～４００質量部の範囲で使用することが好ましい。６００質量部より多いと配合が困難になる上、成形加工性が悪くなるとともに、シートの強度が弱くなる場合がある。 In the present invention, the blending amount of the component (B) may be 0 to 600 parts by mass with respect to 100 parts by mass of the component (A), but it is particularly preferably used in the range of 5 to 400 parts by mass. If the amount is more than 600 parts by mass, blending becomes difficult, the moldability becomes worse, and the strength of the sheet may be weakened.
（Ｃ）成分：
　本発明で使用する（Ｃ）成分であるカーボンブラック粉末は、シリコーンゴムシートの機械的強度、特に加熱時の機械的強度を向上させて耐熱性を向上させると共に、熱伝導性及び導電化することによる帯電防止性を付与するときに用いるものである。 Component (C):
The carbon black powder, which is the component (C) used in the present invention, improves the heat resistance by improving the mechanical strength of the silicone rubber sheet, particularly the mechanical strength during heating, and also makes it thermally conductive and conductive. It is used when imparting antistatic properties due to.
　カーボンブラックは、その製造方法により、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック等に分類され、また、通常、硫黄等の不純物を含むものが多い。本発明においては、水以外の揮発分が０．５質量％以下のものを使用することが好ましい。特にアセチレンブラックは不純物が少ないので好適である。
　上記水以外の揮発分の測定方法は、ＪＩＳ　Ｋ　６２２１の“ゴム用カーボンブラック試験方法”に記載されている。具体的には、るつぼの中にカーボンブラックを規定量入れ、９５０℃で７分間加熱した後の揮発減量を測定する。 Carbon black is classified into furnace black, channel black, thermal black, acetylene black, etc. depending on the production method, and usually contains many impurities such as sulfur. In the present invention, it is preferable to use one having a volatile content other than water of 0.5% by mass or less. In particular, acetylene black is preferable because it has few impurities.
The method for measuring volatile components other than water is described in “Testing method of carbon black for rubber” in JIS K 6221. Specifically, a specified amount of carbon black is put in a crucible, and the volatilization loss after heating at 950 ° C. for 7 minutes is measured.
　また、（Ｃ）成分のカーボンブラックの平均粒径は、１０～３００ｎｍの範囲であることが好ましく、特に１５～１００ｎｍの範囲であることが好ましい。また、ＢＥＴ比表面積は２０～３００ｍ2／ｇであることが好ましく、特に、３０～２００ｍ2／ｇであることが好ましい。カーボンブラックの形状は、粉体、針状いずれでも良い。 The average particle size of the carbon black as the component (C) is preferably in the range of 10 to 300 nm, particularly preferably in the range of 15 to 100 nm. The BET specific surface area is preferably 20 to 300 m 2 / g, and particularly preferably 30 to 200 m 2 / g. The shape of carbon black may be either powder or needle.
　カーボンブラックの平均粒径については、電子顕微鏡を用いて撮影した写真から一次粒子径を測定し、求めた粒子径を算術平均する、いわゆる電子顕微鏡法による平均粒径である。なお、通常、カーボンブラックは一次粒子が凝集して二次粒子を形成しているが、ここで言う平均粒径はその二次粒子の平均粒径ではなく、一次粒子の平均粒径をいう。 The average particle diameter of carbon black is an average particle diameter obtained by so-called electron microscopy, in which the primary particle diameter is measured from a photograph taken using an electron microscope, and the obtained particle diameter is arithmetically averaged. Carbon black usually aggregates primary particles to form secondary particles, but the average particle size referred to here is not the average particle size of the secondary particles but the average particle size of the primary particles.
　本発明における（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対して０～８０質量部であり、特に５～７５質量部の範囲で使用することが好ましい。８０質量部を超えると均一に配合することが困難になる上、得られる組成物の成形加工性が極めて悪くなる場合がある。 In the present invention, the blending amount of the component (C) is 0 to 80 parts by weight with respect to 100 parts by weight of the component (A), and is preferably used in the range of 5 to 75 parts by weight. If it exceeds 80 parts by mass, it may be difficult to mix uniformly, and the molding processability of the resulting composition may be extremely deteriorated.
（Ｄ）成分：
　本発明で使用する（Ｄ）成分であるＢＥＴ比表面積が５０ｍ2／ｇ以上である補強性シリカ粉末としては、親水性又は疎水性のヒュームドシリカ（乾式シリカ）や、沈降シリカ（湿式シリカ）、結晶性シリカ、石英などが挙げられ、これらは１種単独で用いることも２種以上を組み合わせて用いることもできる。ヒュームドシリカや沈降シリカは、補強性の点からＢＥＴ比表面積が５０ｍ2／ｇ以上であることが好ましいが、通常は、５０～８００ｍ2／ｇ、特に１００～５００ｍ2／ｇ程度のものを使用するのが良い。比表面積が５０ｍ2／ｇ未満では、補強効果が十分得られない場合がある。 (D) component:
As the reinforcing silica powder having a BET specific surface area of 50 m 2 / g or more, which is the component (D) used in the present invention, hydrophilic or hydrophobic fumed silica (dry silica), precipitated silica (wet silica) , Crystalline silica, quartz and the like, and these can be used alone or in combination of two or more. Fumed silica and precipitated silica preferably have a BET specific surface area of 50 m 2 / g or more from the viewpoint of reinforcement, but usually have a BET specific surface area of 50 to 800 m 2 / g, particularly about 100 to 500 m 2 / g. Good to use. When the specific surface area is less than 50 m 2 / g, the reinforcing effect may not be sufficiently obtained.
　このようなシリカのうち、市販されている親水性のシリカとしては、Ａｅｒｏｓｉｌ１３０，２００，３００（日本アエロジル（株）又はＤｅｇｕｓｓａ社製の商品名）、ＣａｂｏｓｉｌＭＳ－５，ＭＳ－７（Ｃａｂｏｔ社製の商品名）、ＲｈｅｏｒｏｓｉｌＱＳ－１０２，１０３（トクヤマ（株）製の商品名）、ＮｉｐｓｉｌＬＰ（日本シリカ工業（株）製の商品名）等が挙げられる。また、疎水性シリカとしては、ＡｅｒｏｓｉｌＲ－８１２，Ｒ－８１２Ｓ，Ｒ－９７２，Ｒ－９７４（Ｄｅｇｕｓｓａ社製の商品名）、ＲｈｅｏｒｏｓｉｌＭＴ－１０（トクヤマ（株）製の商品名）、ＮｉｐｓｉｌＳＳシリーズ（日本シリカ工業（株）製の商品名）などが挙げられるが、これらに限定されるわけではない。 Among such silicas, commercially available hydrophilic silicas include Aerosil 130, 200, 300 (Nippon Aerosil Co., Ltd. or Degussa product name), Cabosil MS-5, MS-7 (manufactured by Cabot). Product name), Rheorosil QS-102,103 (product name manufactured by Tokuyama Co., Ltd.), NipsilLP (product name manufactured by Nippon Silica Kogyo Co., Ltd.), and the like. Hydrophobic silica includes Aerosil R-812, R-812S, R-972, R-974 (trade name manufactured by Degussa), Rheorosil MT-10 (trade name manufactured by Tokuyama Corporation), and Nippon Sil series (Japan). The product name is manufactured by Silica Industry Co., Ltd.), but is not limited thereto.
　本発明における（Ｄ）成分の配合量は、（Ａ）成分１００質量部に対して０～５０質量部であるが、５～３５質量部であることがより好ましく、特に１０～３０質量部であることが好ましい。５０質量部より多くなると、シリコーンゴム組成物の可塑度が高くなりすぎて成形性が悪くなったり、硬化後のゴムが硬くなりすぎたりする場合がある。 The blending amount of the component (D) in the present invention is 0 to 50 parts by mass with respect to 100 parts by mass of the component (A), more preferably 5 to 35 parts by mass, particularly 10 to 30 parts by mass. Preferably there is. If it exceeds 50 parts by mass, the plasticity of the silicone rubber composition may become too high, resulting in poor moldability, or the cured rubber may become too hard.
（Ｅ）成分：
　本発明で使用する（Ｅ）成分である硬化剤は、通常シリコーンゴムの硬化に使用されている公知のものの中から適宜選択して使用することができる。このような硬化剤としては、例えば、
　ａ）ラジカル反応に使用されるジ－ｔ－ブチルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ジクミルパーオキサイドなどの有機過酸化物；
　ｂ）（Ａ）成分のオルガノポリシロキサンがアルケニル基を有する場合には、付加反応硬化剤として、ケイ素原子に結合した水素原子を１分子中に２個以上含有するオルガノハイドロジェンポリシロキサンと、白金、パラジウム等の白金族金属系触媒との組合わせ；等が例示される。本発明においては、反応を制御し易いこと、反応残渣が残らないことなどの理由から、ｂ）の付加反応硬化剤の方が好ましいが、必要に応じて両者を併用しても良い。 (E) component:
The curing agent which is the component (E) used in the present invention can be appropriately selected from known ones usually used for curing silicone rubber. As such a curing agent, for example,
a) organic peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide used in radical reactions;
b) When the organopolysiloxane of component (A) has an alkenyl group, an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to a silicon atom in one molecule as an addition reaction curing agent, and platinum And combinations with platinum group metal catalysts such as palladium; and the like. In the present invention, the addition reaction curing agent b) is preferable because the reaction is easy to control and no reaction residue remains, but both may be used together if necessary.
　これらの硬化剤の添加量は、通常のシリコーンゴムの場合と同様にすればよいが、一般的には次の通りである。
　硬化剤ａ）については、（Ａ）成分のオルガノポリシロキサン１００質量部当り、０．１～２０質量部使用することが好ましい。
　硬化剤ｂ）については、前記ケイ素原子に結合した水素原子を１分子中に２個以上含有するオルガノハイドロジェンシロキサンを、（Ａ）成分のアルケニル基１モル当り、該オルガノハイドロジェンシロキサンが有するケイ素原子に結合する水素原子が０．５～５モルとなる量とすると共に、白金族金属系触媒の量が、（Ａ）成分に対して、金属分として０．１～１，０００ｐｐｍ（質量基準）となる範囲が好ましい。 The addition amount of these curing agents may be the same as in the case of ordinary silicone rubber, but is generally as follows.
The curing agent a) is preferably used in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A) organopolysiloxane.
With respect to the curing agent b), silicon having an organohydrogensiloxane containing two or more hydrogen atoms bonded to the silicon atom in one molecule per mole of the alkenyl group of the component (A). The amount of hydrogen atoms bonded to the atoms is 0.5 to 5 mol, and the amount of the platinum group metal catalyst is 0.1 to 1,000 ppm (mass basis) as a metal component with respect to the component (A). ) Is preferred.
その他の成分：
　本発明のシリコーンゴム組成物には、必要に応じて更に、酸化セリウム、ベンガラ、酸化チタン等の耐熱付与剤、クレイ、炭酸カルシウム、けいそう土、二酸化チタン等の充填剤、低分子シロキサンエステル、シラノール等の分散剤、シランカップリング剤、チタンカップリング剤等の接着付与剤、難燃性を付与させる白金族金属系化合物、ゴムコンパウンドのグリーン強度を上げるテトラフルオロポリエチレン粒子、ガラス繊維、アラミド繊維等の補強性繊維などを添加してもよい。 Other ingredients:
In the silicone rubber composition of the present invention, if necessary, heat resistance imparting agents such as cerium oxide, bengara and titanium oxide, fillers such as clay, calcium carbonate, diatomaceous earth and titanium dioxide, low molecular siloxane esters, Dispersants such as silanol, adhesion imparting agents such as silane coupling agents, titanium coupling agents, platinum group metal compounds that impart flame retardancy, tetrafluoropolyethylene particles that increase the green strength of rubber compounds, glass fibers, aramid fibers Reinforcing fibers such as may be added.
［調製・加工］
　本発明に用いるシリコーンゴム組成物は、上述した各成分を、二本ロールミル、ニーダー、バンバリーミキサー、プラネタリーミキサー等の混合機を用いて混練りすればよいが、一般的には、硬化剤だけを使用する直前に添加すれば良いように、他の成分を予め混練しておくことが好ましい。
　本発明の太陽電池セル電極の接続用シートであるシリコーンゴムシートの成形方法としては、硬化剤までの全ての成分を配合したシリコーンゴム組成物を、カレンダーあるいは押出し機で所定の厚さに分出ししてから硬化させる方法、液状のシリコーンゴム組成物あるいはトルエン等の溶剤に溶解して液状化したシリコーンゴム組成物を、フィルム上にコーティングしてから硬化させる方法等が挙げられる。 [Preparation and processing]
The silicone rubber composition used in the present invention may be prepared by kneading the above-described components using a mixer such as a two-roll mill, a kneader, a Banbury mixer, or a planetary mixer. It is preferable to knead the other components in advance so that it may be added immediately before use.
As a method for forming a silicone rubber sheet, which is a solar cell electrode connection sheet of the present invention, a silicone rubber composition containing all components up to a curing agent is dispensed to a predetermined thickness with a calendar or an extruder. And a method of curing after coating a film with a liquid silicone rubber composition or a silicone rubber composition dissolved in a solvent such as toluene and liquefied.
［シリコーンゴムの特性］
　シリコーンゴムシートの適度なクッション性を確保するため、シリコーンゴム組成物の硬化後の切断時の伸びと硬さは以下のような特徴を有することが好ましい。
　２３℃の室温における切断時の伸びは、４０～１，０００％が好ましく、６０～３００％であることがより好ましい。特に好ましくは７０～１５０％である。基本的には、接続部材の位置ズレを避けるために伸びは小さいほうが良いが、伸びが４０％未満ではシートの柔軟性に欠けるため、被圧着部に凹凸や段差があった場合に、その形状に追随できずに均一な圧力での圧着ができなくなるとともに、応力を分散することができなくなり、切れ易くなったり、シートに対して折り曲げ方向の力がかかった場合に、シートが破断したりするという問題が発生するおそれがある。 [Characteristics of silicone rubber]
In order to secure an appropriate cushioning property of the silicone rubber sheet, it is preferable that the elongation and hardness at the time of cutting after curing of the silicone rubber composition have the following characteristics.
The elongation at cutting at a room temperature of 23 ° C. is preferably 40 to 1,000%, and more preferably 60 to 300%. Particularly preferred is 70 to 150%. Basically, the elongation should be small in order to avoid misalignment of the connecting member, but if the elongation is less than 40%, the sheet lacks flexibility. The sheet cannot be pressed with a uniform pressure without being able to follow, and the stress cannot be dispersed, making it easy to break, or the sheet breaks when a force in the bending direction is applied to the sheet. May occur.
　また、タイプＡデュロメーターで測定した２３℃の室温における硬さが、１０～９０であることが好ましく、特に４０～８５であることが好ましい。この硬さは、位置ずれ防止と共に、被圧着物の平面度、平坦度、或いは平行度の公差を補正して均一な圧力を伝達するためのクッション性を両立させるものである。 The hardness at room temperature of 23 ° C. measured with a type A durometer is preferably 10 to 90, and particularly preferably 40 to 85. This hardness is compatible with cushioning for transmitting a uniform pressure by correcting the tolerance of flatness, flatness, or parallelism of the object to be pressed together with preventing displacement.
補強材
　上記した太陽電池セル電極の接続用シートは、無機物及び／又は耐熱性樹脂からなるクロス及び／又は繊維で補強されていても良い。例えば、無機物からなる繊維としては、ガラス繊維、炭素繊維、ステンレス繊維などが、耐熱性樹脂からなる繊維としては、アラミド繊維、アミド繊維、テトラフルオロポリエチレンなどのフッ素樹脂繊維などが挙げられるが、これらに限定されるものではない。補強の方法としては、これらの繊維をポリマー中に混練しても良いし、これらの繊維を編んでクロスとしたものを中間層あるいは片面に積層しても良く、これらの方法に限定されるものではない。繊維材で補強することにより、シートの面方向の伸びが抑制され、配線部材接続装置の加熱・加圧部材からの圧力を確実に導電性接着部材に伝えることができると共に、破れに対する耐性が格段に向上する。 Reinforcing Material The solar cell electrode connection sheet described above may be reinforced with a cloth and / or fiber made of an inorganic material and / or a heat-resistant resin. For example, glass fibers, carbon fibers, stainless fibers, etc. are used as the fibers made of inorganic materials, and fluororesin fibers such as aramid fibers, amide fibers, tetrafluoropolyethylene, etc. are used as the fibers made of the heat resistant resin. It is not limited to. As a reinforcing method, these fibers may be kneaded in a polymer, or a cross made by knitting these fibers may be laminated on an intermediate layer or one side, and is limited to these methods. is not. Reinforcement with fiber material suppresses the elongation in the surface direction of the sheet, and can reliably transmit the pressure from the heating / pressurizing member of the wiring member connecting device to the conductive adhesive member, and also has a great resistance to tearing. To improve.
　また、本発明の太陽電池セル電極の接続用シートは、加熱・加圧時に、配線部材接続装置の加熱・加圧部材、配線部材、はみ出した導電性接着材料などと直接接触する。導電性接着材料としては、絶縁性樹脂と導電性粒子とを含有するものや、はんだが使用される。加熱・圧着時に使用される太陽電池セル電極の接続用シートは、３００℃以上の高温で使用される場合が多く、これら直接接触する部材に貼り付いて破れてしまうことがあるため、シート表面が直接接触する各種部材へ悪影響を与えずに、非接着性を有していることが好ましい。 Also, the solar cell electrode connection sheet of the present invention is in direct contact with the heating / pressurizing member of the wiring member connecting device, the wiring member, the protruding conductive adhesive material, etc. during heating / pressurization. As the conductive adhesive material, a material containing an insulating resin and conductive particles, or solder is used. The solar cell electrode connection sheet used at the time of heating and pressure bonding is often used at a high temperature of 300 ° C. or more, and may be stuck to these directly contacting members and torn. It is preferable to have non-adhesiveness without adversely affecting various members that are in direct contact.
太陽電池セル電極の接続用シートの熱伝導率
　本発明の太陽電池セル電極の接続用シートには、配線部材接続装置の加熱・加圧部材からの熱を導電性接着材料に伝える役割があるため、この観点からは、熱伝導率が高いほうが好ましい。２３℃の室温における熱伝導率は、０．３Ｗ／ｍＫ以上であることが好ましく、さらに０．４Ｗ／ｍＫ以上であることが好ましく、特には０．６Ｗ／ｍＫ以上であることが好ましい。０．３Ｗ／ｍＫよりも低いと、導電性接着材料に熱が伝わり難いため、加熱・加圧部材の温度を上げなくてはならない。加熱・加圧部材の温度を上げるためには、配線部材接続装置への負担が重くなるし、本接続方式のコストメリットが無くなる場合がある。また、より高温の加熱・加圧部材が太陽電池セル電極の接続用シートに接触するため、シートの熱劣化が促進される場合がある。さらには、高温の加熱・加圧部材が半導体素子上の導電性電極膜に輻射熱を与えるため、太陽電池セルに問題を引き起こすこともある。一方、熱伝導率が５Ｗ／ｍＫを超えると熱伝導性粉末の配合が困難となると共に、シート強度が弱くなりすぎて使用に耐えなくなるため、５Ｗ／ｍＫ以下であることが好ましい。 Thermal conductivity of solar cell electrode connection sheet The solar cell electrode connection sheet of the present invention has a role of transferring heat from the heating / pressurizing member of the wiring member connecting device to the conductive adhesive material. From this viewpoint, it is preferable that the thermal conductivity is high. The thermal conductivity at room temperature of 23 ° C. is preferably 0.3 W / mK or more, more preferably 0.4 W / mK or more, and particularly preferably 0.6 W / mK or more. If it is lower than 0.3 W / mK, it is difficult for heat to be transferred to the conductive adhesive material, so the temperature of the heating / pressurizing member must be raised. In order to raise the temperature of the heating / pressurizing member, the burden on the wiring member connecting device becomes heavy, and the cost merit of this connection method may be lost. Moreover, since a higher temperature heating / pressurizing member comes into contact with the solar cell electrode electrode connection sheet, thermal deterioration of the sheet may be promoted. Furthermore, since the high-temperature heating / pressurizing member gives radiant heat to the conductive electrode film on the semiconductor element, it may cause a problem in the solar battery cell. On the other hand, if the thermal conductivity exceeds 5 W / mK, blending of the thermal conductive powder becomes difficult, and the sheet strength becomes too weak to withstand use, so that it is preferably 5 W / mK or less.
積層品
　本発明の太陽電池セル電極の接続用シートは、本発明の太陽電池セル電極の接続用シートの中から、それぞれ異なる組成からなる２種以上のシート層を積層した構造とすることもできる。例えば、ポリイミドとシリコーンゴム、テトラフルオロポリエチレンとシリコーンゴム、ガラスクロスにテトラフルオロポリエチレンをコートしたものとシリコーンゴム、互いに組成の異なるシリコーンゴム２層以上、フッ素ゴムとシリコーンゴムなど、２層以上の積層シートとしても良いが、これらに限定されるものではない。また、無機物及び／又は耐熱性樹脂からなるクロス及び／又は繊維で補強したシートと補強していないシートを積層しても良いが、これらに限定されるものではない。積層することで、各種シートの利点を組み合わせることができる。 Laminated product The solar cell electrode connection sheet of the present invention can also have a structure in which two or more types of sheet layers having different compositions are laminated from the solar cell electrode connection sheet of the present invention. . For example, polyimide and silicone rubber, tetrafluoropolyethylene and silicone rubber, glass cloth coated with tetrafluoropolyethylene and silicone rubber, two or more layers of silicone rubber with different compositions, fluorine rubber and silicone rubber, etc. Although it is good also as a sheet | seat, it is not limited to these. Moreover, although the sheet | seat reinforced with the cloth | cross and / or fiber which consist of an inorganic substance and / or a heat resistant resin, and the sheet | seat which is not reinforced may be laminated | stacked, it is not limited to these. By laminating, the advantages of various sheets can be combined.
太陽電池セル電極の接続用シートの厚さ
　本発明の太陽電池セル電極の接続用シートの厚さは、０．０１～１ｍｍであることが好ましい。その材質が耐熱性樹脂である場合には、０．０１～０．５ｍｍであり、特に０．０２～０．２ｍｍの範囲であることが好ましい。厚さが０．０１ｍｍ未満では、強度が弱すぎて破れ易いとともに、取扱性が悪くなる場合がある。一方、０．５ｍｍを超えると熱の伝わり方が悪くなる場合がある。シートの材質がフッ素ゴム、シリコーンゴムの場合には、０．０５～１ｍｍであり、特に０．１～０．５ｍｍの範囲であることが好ましい。厚さが０．０５ｍｍ未満では、クッション性が十分でなく、均一な圧力伝達が不可能になる場合がある。一方、１ｍｍを超える厚さになると熱の伝わり方が悪くなる場合がある。
　本発明の太陽電池セル電極の接続用シートの厚さが０．０１～０．２ｍｍと薄い場合には、熱伝導率が０．３Ｗ／ｍＫより小さくても、必要とするシート厚さ方向の熱伝導性能が確保できることがあるため、必ずしも熱伝導率が０．３Ｗ／ｍＫ以上である必要はない。 Thickness of Solar Cell Cell Electrode Connection Sheet The thickness of the solar cell electrode connection sheet of the present invention is preferably 0.01 to 1 mm. When the material is a heat-resistant resin, it is preferably 0.01 to 0.5 mm, particularly preferably 0.02 to 0.2 mm. If the thickness is less than 0.01 mm, the strength is too weak and easily broken, and the handleability may be deteriorated. On the other hand, if the thickness exceeds 0.5 mm, the way of heat transfer may deteriorate. When the material of the sheet is fluororubber or silicone rubber, the thickness is 0.05 to 1 mm, particularly preferably 0.1 to 0.5 mm. If the thickness is less than 0.05 mm, the cushioning property is not sufficient, and uniform pressure transmission may be impossible. On the other hand, if the thickness exceeds 1 mm, the heat transfer may be worse.
When the thickness of the solar cell electrode connection sheet of the present invention is as thin as 0.01 to 0.2 mm, even if the thermal conductivity is less than 0.3 W / mK, the required sheet thickness direction Since heat conduction performance may be ensured, the heat conductivity is not necessarily 0.3 W / mK or more.
接続方法
　本発明の太陽電池セル電極の接続方法は、太陽電池セルの電力を取り出すための電極と配線部材とを、導電性接着材料を介して加熱及び加圧して接続する工程において、配線部材接続装置の加熱及び加圧部材と配線部材との間に、本発明の太陽電池セル電極の接続用シートを介在させて加熱及び加圧するものである。
　導電性接着材料は、例えば、絶縁性樹脂及び導電性粒子を含有したフィルム状又はペースト状のものを別に用意して、接続前に太陽電池セルの電力を取り出すための電極部材上に配置して使用しても良いし、予めこの材料を配線部材上に成形したものを使用しても良い。予め配線部材上に導電性接着材料を成形したものを使用する場合、接続工程を短縮できる。はんだめっきした配線部材を使用する場合には、めっきのはんだを導電性接着材料として使用して、別の導電性接着材料を設置せずに使用することができる。はんだめっきした配線部材を使用する場合には、別に絶縁性樹脂及び導電性粒子を含有した導電性樹脂接着材料を用いて、はんだが溶融しない条件で接続しても良いし、はんだめっきのはんだと、絶縁性樹脂及び導電性粒子を含有した導電性接着材料との両者を導電性接着材料として機能させて、併用して接続しても良い。 Connection Method The solar cell electrode connection method of the present invention is a wiring member connection in the step of connecting the electrode and the wiring member for taking out the electric power of the solar cell by heating and pressurizing via a conductive adhesive material. Heating and pressurization are performed by interposing the solar cell electrode connection sheet of the present invention between the heating and pressurizing member of the apparatus and the wiring member.
For example, the conductive adhesive material is prepared separately in the form of a film or paste containing an insulating resin and conductive particles, and placed on the electrode member for taking out the electric power of the solar battery cell before connection. You may use, and you may use what shape | molded this material on the wiring member previously. When using what formed the conductive adhesive material on the wiring member beforehand, a connection process can be shortened. When using a solder-plated wiring member, the plating solder can be used as a conductive adhesive material without using another conductive adhesive material. When using a solder-plated wiring member, it may be connected under the condition that the solder does not melt by using a conductive resin adhesive material containing an insulating resin and conductive particles. Further, both the insulating resin and the conductive adhesive material containing conductive particles may function as a conductive adhesive material and may be connected in combination.
　本発明の接続方法は、最適化された本発明による太陽電池セル電極の接続用シートを加熱及び加圧部材と配線部材の間に介在させて使用することから、加熱・加圧部材全面を均一な温度・圧力で圧着できるとともに、はみ出した導電性接着材料と加熱及び加圧部材との貼り付きを防止したり、導電性接着材料が加熱及び加圧部材上に堆積することを防止したりすることが可能となる。また、加熱及び加圧部材は、通常、金属製の硬いものであるため、接続用シートは、圧着時の加熱及び加圧部材からの衝撃を和らげ、太陽電池セルの割れを防ぐ役割を担うこともできる。 The connection method of the present invention uses the optimized solar cell electrode connection sheet according to the present invention interposed between the heating and pressure member and the wiring member, so that the entire surface of the heating and pressure member is uniform. It can be pressure-bonded at various temperatures and pressures, and can prevent sticking between the protruding conductive adhesive material and the heating and pressing member, or prevent the conductive adhesive material from depositing on the heating and pressing member. It becomes possible. In addition, since the heating and pressing members are usually hard metal, the connecting sheet plays a role of mitigating the impact from the heating and pressing members during crimping and preventing cracking of the solar cells. You can also.
　本発明の太陽電池セル電極の接続条件は、太陽電池の種類と構造及びそれに合わせた導電性接着材料によって最適化されるが、絶縁性樹脂及び導電性粒子を含有した導電性樹脂接着材料を使用する場合の典型的な条件範囲としては、導電性樹脂接着材料の加熱温度は１３０～２２０℃、そのときの加熱及び加圧部材の温度は２００～４００℃、圧力は１～５ＭＰａ、圧着時間は３～３０秒であるが、この範囲に限定されるものではない。 The connection condition of the solar cell electrode of the present invention is optimized by the type and structure of the solar cell and the conductive adhesive material matched to the solar cell electrode, but the conductive resin adhesive material containing the insulating resin and conductive particles is used. As a typical condition range, the heating temperature of the conductive resin adhesive material is 130 to 220 ° C., the temperature of the heating and pressurizing member is 200 to 400 ° C., the pressure is 1 to 5 MPa, and the pressure bonding time is Although it is 3 to 30 seconds, it is not limited to this range.
　太陽電池セルの電極と配線部材との接続は、個々の電極と配線部材との接続を、それぞれ別に行っても良いが、太陽電池セルからの電力を取り出すための表面電極と裏面電極が設けられたセルの場合には、表面電極及び配線部材と、裏面電極及び他の配線部材とを同時に加熱及び加圧する方法の方が、生産効率が向上するため好ましい。 The connection between the electrode of the solar battery cell and the wiring member may be performed separately for each electrode and the wiring member, but a front electrode and a back electrode for taking out electric power from the solar battery cell are provided. In the case of a cell, the method of simultaneously heating and pressurizing the front surface electrode and the wiring member, and the back surface electrode and the other wiring member is preferable because the production efficiency is improved.
太陽電池モジュール
　本発明の太陽電池モジュールは、単一又は複数の太陽電池セルが配列され、互いに隣接する前記太陽電池セルの電力を取り出すための電極と配線部材が、本発明の太陽電池セル電極の接続方法によって接続されたものである。 Solar cell module The solar cell module of the present invention has a single or multiple solar cells arranged, and an electrode and a wiring member for taking out the electric power of the solar cells adjacent to each other are the solar cell electrodes of the present invention. Connected according to the connection method.
　本発明の太陽電池モジュールは、太陽電池セルの電力を取り出すための電極と配線部材とを、導電性接着材料を介して加熱及び加圧して接続する工程で、加熱及び加圧部材と配線部材の間に最適化された太陽電池セル電極の接続用シートを介在させて製造され、例えば、図２に示す構造を有する。ここで、図２ａは太陽電池セル接続の一例（太陽電池モジュールの一部分）を示す平面図、ｂは断面図、ｃは太陽電池セルの断面拡大図であり、１はシリコン基板、２は電極、３は導電性接着材料、４は配線部材を示し、１０は太陽電池セルを示す。
　本発明においては、加熱・加圧部全面を均一な温度・圧力での圧着が可能となり、本発明により得られる太陽電池モジュールは、接点不良がなく、高品質で長期耐久性も良好なものとなる。特に、導電性接着材料として、絶縁性樹脂及び導電性粒子を含有したものを使用する場合には、反りや割れのない太陽電池セルとすることができる。 The solar cell module of the present invention is a process of connecting an electrode for extracting electric power of a solar battery cell and a wiring member by heating and pressurizing via a conductive adhesive material. It is manufactured with a sheet for connecting solar cell electrodes optimized in between, and has, for example, the structure shown in FIG. Here, FIG. 2a is a plan view showing an example of a solar cell connection (a part of the solar cell module), b is a cross-sectional view, c is a cross-sectional enlarged view of the solar cell, 1 is a silicon substrate, 2 is an electrode, 3 is a conductive adhesive material, 4 is a wiring member, and 10 is a solar cell.
In the present invention, the entire surface of the heating / pressurizing part can be crimped at a uniform temperature / pressure, and the solar cell module obtained by the present invention has no contact failure, high quality and good long-term durability. Become. In particular, when a conductive adhesive material containing an insulating resin and conductive particles is used, a solar battery cell free from warping or cracking can be obtained.
　以下、実施例及び比較例を示し、本発明をより具体的に説明するが、本発明は下記の実施例に制限されるものではない。 Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.
　［実施例１～６］
　下記成分を表１に示す割合（質量部）で配合して太陽電池セル電極の接続用シートとした。
（Ａ）オルガノポリシロキサン：
　（ａ－１）ジメチルシロキサン単位９９．８５モル％及びメチルビニルシロキサン単位０．１５モル％からなる、平均重合度が８，０００の、分子鎖両末端がジメチルビニルシロキシ基で封鎖されたメチルビニルポリシロキサン
　（ａ－２）ジメチルシロキサン単位９９．５モル％及びメチルビニルシロキサン単位０．５モル％からなる、平均重合度が８，０００の、分子鎖両末端がジメチルビニルシロキシ基で封鎖されたメチルビニルポリシロキサン
（Ｂ）熱伝導性充填剤：
　（ｂ－１）平均粒径が５μｍの金属ケイ素粉砕粉末（表面に強制酸化処理をしたもの）
　（ｂ－２）平均粒径が４μｍの結晶性二酸化ケイ素粉砕粉末
　（ｂ－３）平均粒径が４μｍの酸化アルミニウム粉砕粉末
（Ｃ）カーボンブラック粉末：
　（ｃ－１）平均粒径が３５ｎｍ、水以外の揮発分が０．１０質量％、ＢＥＴ比表面積が６９ｍ2／ｇのアセチレンブラック
（Ｄ）補強性シリカ微粉末：
　（ｄ－１）ＢＥＴ比表面積が３００ｍ2／ｇの補強性シリカ微粉末（商品名：Ａｅｒｏｓｉｌ３００、日本アエロジル（株）製）
（Ｅ）硬化剤：
　（ｅ－１）塩化白金酸のビニルシロキサン錯体（白金含有量１質量％）
　（ｅ－２）下記式（１）で表されるメチルハイドロジェンポリシロキサン
Figure JPOXMLDOC01-appb-C000001
 　（ｅ－３）有機過酸化物：Ｃ－８（信越化学工業（株）製）
　（ｅ－４）有機過酸化物：Ｃ－２３（信越化学工業（株）製）
その他の成分：
　（ｆ－１）ジメチルジメトキシシラン
　（ｇ－１）ＢＥＴ比表面積が１４０ｍ2／ｇの酸化セリウム粉末
　（ｈ－１）エチニルシクロヘキサノール [Examples 1 to 6]
The following components were blended in the proportions (mass parts) shown in Table 1 to obtain a solar cell electrode connection sheet.
(A) Organopolysiloxane:
(A-1) Methylvinyl consisting of 99.85 mol% of dimethylsiloxane units and 0.15 mol% of methylvinylsiloxane units, having an average degree of polymerization of 8,000, and having both molecular chain ends blocked with dimethylvinylsiloxy groups Polysiloxane (a-2) Consisting of 99.5 mol% of dimethylsiloxane units and 0.5 mol% of methylvinylsiloxane units, the average degree of polymerization was 8,000, and both ends of the molecular chain were blocked with dimethylvinylsiloxy groups Methyl vinyl polysiloxane
(B) Thermally conductive filler:
(B-1) Metallic silicon pulverized powder having an average particle size of 5 μm (surface subjected to forced oxidation treatment)
(B-2) Crystalline silicon dioxide pulverized powder having an average particle size of 4 μm (b-3) Aluminum oxide pulverized powder having an average particle size of 4 μm
(C) Carbon black powder:
(C-1) Acetylene black having an average particle size of 35 nm, a volatile content other than water of 0.10% by mass, and a BET specific surface area of 69 m 2 / g
(D) Reinforcing silica fine powder:
(D-1) Reinforcing silica fine powder having a BET specific surface area of 300 m 2 / g (trade name: Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.)
(E) Curing agent:
(E-1) Vinylsiloxane complex of chloroplatinic acid (platinum content 1% by mass)
(E-2) Methyl hydrogen polysiloxane represented by the following formula (1)
Figure JPOXMLDOC01-appb-C000001
 (E-3) Organic peroxide: C-8 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(E-4) Organic peroxide: C-23 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Other ingredients:
(F-1) Dimethyldimethoxysilane (g-1) Cerium oxide powder having a BET specific surface area of 140 m 2 / g (h-1) Ethynylcyclohexanol
組成物の調製及び成形
　下記のように組成物を調製し、シート状に成形した。
　（Ｄ）成分が配合される場合には、（Ａ）成分、（Ｄ）成分と（Ｄ）成分の表面処理剤として（ｆ－１）成分とイオン交換水を、ニーダーを用いて１７０℃で２時間加熱しながら配合・混練りして均一化した。（Ｄ）成分がゼロの場合には、この工程は行わない。
　得られた混合物又は（Ａ）成分に対して、（Ｂ）成分、（Ｃ）成分と必要に応じて（ｇ－１）成分を加え、加圧ニーダーを用いて１５分間配合・混練りして均一化した。
　更に、付加反応硬化タイプの場合には、（ｅ－１）成分、（ｈ－１）成分、（ｅ－２）成分を、順次二本ロールミルで混練りしながら上記の順序で添加し、硬化性シリコーンゴム組成物を調製した。ラジカル反応硬化タイプの場合には、（ｅ－３）又は（ｅ－４）成分を二本ロールミルで混練りして、硬化性シリコーンゴム組成物を調製した。
　カレンダー成形機を用いて、得られた硬化性シリコーンゴム組成物を厚さ０．２５ｍｍに分出ししてから、厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上に転写した。ＰＥＴフィルムとの積層品の状態のまま、付加反応硬化タイプの場合には１５０℃の、ラジカル反応硬化タイプの場合には１６０℃の加熱炉中を５分間通して、シート状のシリコーンゴム組成物を硬化させた。得られたシート状組成物からＰＥＴフィルムを剥離し、２００℃の乾燥機中で４時間熱処理して、厚さが０．２０～０．４５ｍｍのシリコーンゴムシートを作製した。 Preparation and Molding of Composition A composition was prepared as described below and molded into a sheet.
When component (D) is blended, component (f-1) and ion-exchanged water are used as a surface treatment agent for component (A), component (D) and component (D) at 170 ° C. using a kneader. The mixture was kneaded and kneaded while heating for 2 hours. When the component (D) is zero, this step is not performed.
Add component (B), component (C) and component (g-1) as necessary to the resulting mixture or component (A) and blend and knead for 15 minutes using a pressure kneader. Homogenized.
Further, in the case of addition reaction curing type, the components (e-1), (h-1), and (e-2) are added in the above order while kneading sequentially with a two-roll mill, and cured. A functional silicone rubber composition was prepared. In the case of the radical reaction curing type, the (e-3) or (e-4) component was kneaded with a two-roll mill to prepare a curable silicone rubber composition.
The obtained curable silicone rubber composition was dispensed to a thickness of 0.25 mm using a calendar molding machine, and then transferred onto a polyethylene terephthalate (PET) film having a thickness of 100 μm. The sheet-like silicone rubber composition is passed through a heating furnace at 150 ° C. in the case of the addition reaction curing type and 160 ° C. in the case of the radical reaction curing type for 5 minutes while being in the state of a laminate with the PET film. Was cured. The PET film was peeled from the obtained sheet-like composition, and heat-treated in a dryer at 200 ° C. for 4 hours to produce a silicone rubber sheet having a thickness of 0.20 to 0.45 mm.
［シリコーンゴムシートの基本物性の評価］
　硬さ、切断時伸びを、ＪＩＳ　Ｋ６２４９の規定に準拠して測定した。但し、硬さについては、タイプＡデュロメーターを用いて作製したシートを、厚さが６ｍｍ以上となるように重ねて測定した。切断時伸びは、ダンベル状２号形の試験片を使用して測定した。
　また、熱伝導率はＡＳＴＭ　Ｅ　１５３０の規定に準拠して測定した。
　結果を表１に示した。 [Evaluation of basic physical properties of silicone rubber sheet]
Hardness and elongation at break were measured in accordance with JIS K6249. However, the hardness was measured by stacking sheets prepared using a type A durometer so that the thickness was 6 mm or more. The elongation at break was measured using a dumbbell-shaped No. 2 test piece.
Further, the thermal conductivity was measured in accordance with ASTM E 1530.
The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１～６で得られたシリコーンゴムシート及び下記実施例７～１１、比較例２，３のシートにつき、太陽電池セルを用いて下記接続実験を行い、評価した。結果を表２に示す。 For the silicone rubber sheets obtained in Examples 1 to 6, and the sheets of Examples 7 to 11 and Comparative Examples 2 and 3 below, the following connection experiments were performed using solar cells and evaluated. The results are shown in Table 2.
　［実施例７］
　厚さ１３０μｍの単層ＰＴＦＥフィルム：ニトフロンフィルム（日東電工（株）製商品名、融点３２７℃、熱伝導率０．２Ｗ／ｍＫ）を用いた。 [Example 7]
A single-layer PTFE film having a thickness of 130 μm: Nitoflon film (trade name, manufactured by Nitto Denko Corporation, melting point 327 ° C., thermal conductivity 0.2 W / mK) was used.
　［実施例８］
　厚さ４５μｍのガラスクロスで補強したＰＴＦＥフィルム：ニトフロン含浸ガラスクロス（日東電工（株）製商品名、融点３２７℃、熱伝導率０．３Ｗ／ｍＫ）を用いた。 [Example 8]
PTFE film reinforced with a 45 μm thick glass cloth: Nitoflon-impregnated glass cloth (trade name, manufactured by Nitto Denko Corporation, melting point 327 ° C., thermal conductivity 0.3 W / mK) was used.
　［実施例９］
　厚さ５０μｍのポリイミドフィルム：カプトン２００Ｈ（東レ・デュポン（株）製商品名、融点、ガラス転移温度なし、熱伝導率０．２Ｗ／ｍＫ）を用いた。 [Example 9]
Polyimide film having a thickness of 50 μm: Kapton 200H (trade name, manufactured by Toray DuPont Co., Ltd., melting point, no glass transition temperature, thermal conductivity 0.2 W / mK) was used.
　［実施例１０］
　実施例８の厚さ４５μｍのガラスクロスで補強したＰＴＦＥフィルムをＰＥＴフィルムの代わりに使用して、プラズマ処理したガラスクロスで補強したＰＴＦＥフィルム面上に実施例１の組成のシリコーンゴム層を加熱硬化させて積層し、シート総厚が０．２５ｍｍのガラスクロスで補強したＰＴＦＥフィルムとシリコーンゴム層を積層した２層構造の複合シートを作製した。
　ガラスクロスで補強したＰＴＦＥフィルム側の面を太陽電池セル側として接続実験を行った。 [Example 10]
The PTFE film reinforced with a 45 μm thick glass cloth of Example 8 was used in place of the PET film, and the silicone rubber layer having the composition of Example 1 was heat-cured on the surface of the PTFE film reinforced with the plasma-treated glass cloth. A composite sheet having a two-layer structure in which a PTFE film reinforced with a glass cloth having a total sheet thickness of 0.25 mm and a silicone rubber layer were laminated was prepared.
The connection experiment was conducted with the PTFE film side surface reinforced with glass cloth as the solar cell side.
　［実施例１１］
　実施例１の組成の層を厚さ０．２５ｍｍで成形し、重ねて実施例６の組成の層を０．１ｍｍの厚さで積層して、シート総厚が０．３５ｍｍとなるようにしてシートを作製した。
　実施例６の組成の層側を太陽電池セル側として接続実験を行った。 [Example 11]
The layer having the composition of Example 1 was formed to a thickness of 0.25 mm, and the layer having the composition of Example 6 was laminated to a thickness of 0.1 mm so that the total thickness of the sheet was 0.35 mm. A sheet was produced.
A connection experiment was conducted with the layer side of the composition of Example 6 as the solar cell side.
　［比較例１］
　シートを使用しないで接続実験を行った。 [Comparative Example 1]
A connection experiment was conducted without using a sheet.
　［比較例２］
　厚さ５０μｍのアルミ箔を使用した。 [Comparative Example 2]
An aluminum foil having a thickness of 50 μm was used.
　［比較例３］
　厚さ１３０μｍのガラスクロスを使用した。 [Comparative Example 3]
A glass cloth having a thickness of 130 μm was used.
　［接続実験］
　電力取り出し用の電極として、幅２ｍｍの銀系バスバー集電電極が配線部材接続用の表面電極及び裏面電極として設けられた幅１５０ｍｍ×長さ１５０ｍｍ×厚さ１６０μｍのシリコン多結晶太陽電池セルを準備した。
　配線部材として、幅２ｍｍ×厚さ１６０μｍの平角形の断面形状の帯状の銅箔線とその銅箔線にはんだめっきした帯状のはんだめっき銅箔線を準備した。
　導電性接着材料として、エポキシ系絶縁接着剤に平均粒径６μｍの表面に金めっきしたニッケル粒子を配合した組成物を、幅２ｍｍ×厚さ４５μｍのフィルム状に成形したものを準備した。 [Connection experiment]
As a power extraction electrode, a 2 mm wide silver-based bus bar current collecting electrode is provided as a front electrode and a back electrode for connecting a wiring member, and a 150 mm wide x 150 mm thick silicon polycrystalline solar cell is prepared. did.
As wiring members, a strip-shaped copper foil wire having a rectangular cross section with a width of 2 mm and a thickness of 160 μm, and a strip-shaped solder-plated copper foil wire solder-plated on the copper foil wire were prepared.
As the conductive adhesive material, a composition in which an epoxy insulating adhesive was mixed with nickel particles plated with gold on the surface having an average particle diameter of 6 μm and formed into a film shape having a width of 2 mm and a thickness of 45 μm was prepared.
　さらに、太陽電池セル電極の接続用シートとして表２に示す実施例１～１１及び比較例２，３のシートを準備し、上記シリコン多結晶太陽電池セルの表面電極及び裏面電極と配線部材との接続を行った。
　また、比較例１として、シートを使用せずに接続を行った。 Further, sheets of Examples 1 to 11 and Comparative Examples 2 and 3 shown in Table 2 were prepared as connecting sheets for solar cell electrodes, and the front and back electrodes of the silicon polycrystalline solar cell and the wiring member were prepared. Connected.
Further, as Comparative Example 1, connection was performed without using a sheet.
　接続は、表面電極及び裏面電極の両面を同時に接続できる配線部材接続装置を使用し、図１に示したように、シリコン基板１上の電極２と配線部材４の間に上記導電性接着材料であるフィルム３を挟み、配線部材上に電極接続用シート５を配置して、その上から、装置の加熱及び加圧部材６で圧着した。圧着条件は、導電性接着材料が１９０℃となるように加熱及び加圧部材の設定温度を調節し、３ＭＰａで１０秒間とした。このとき、加熱及び加圧部材の表面温度は、いずれのシートを使用した場合、あるいはシートを使用しない場合でも３００℃を超えていた。 For the connection, a wiring member connecting device capable of simultaneously connecting both the front surface electrode and the back surface electrode is used, and the conductive adhesive material is used between the electrode 2 on the silicon substrate 1 and the wiring member 4 as shown in FIG. An electrode connecting sheet 5 was placed on the wiring member with a certain film 3 interposed therebetween, and the device was pressure-bonded by the heating and pressure member 6 of the apparatus. The pressure bonding conditions were set to 10 MPa at 3 MPa by adjusting the set temperature of the heating and pressure member so that the conductive adhesive material was 190 ° C. At this time, the surface temperature of the heating and pressing member exceeded 300 ° C. even when any sheet was used or when no sheet was used.
［接続実験結果の評価項目］
（１）接続部の均一性の評価
　太陽電池セルの全長：長さ１５０ｍｍ全部の接続部の断面を顕微鏡観察し、均一かつ不良部分がないかどうかを評価した。はんだめっき銅箔線を使用した。
（２）接続抵抗の合格率
　一つの種類のシートに対して、１００枚の太陽電池セルの電極への配線部材の接続を行い、各電極と配線部材間の接続抵抗が使用可能レベルかどうかを確認し、合格率を評価した。銅箔線を使用した。
（３）セル割れの発生確率
　一つの種類のシートに対して、１００枚の太陽電池セルの電極への配線部材の接続を行い、セル割れの発生確率を評価した。銅箔線を使用した。
（４）装置の加熱及び加圧部材表面の汚れ評価
　一つの種類のシートに対して、１００枚の太陽電池セルの電極への配線部材の接続を行い、加熱及び加圧部材表面の汚れを評価した。はんだめっき銅箔線を使用した。
（５）太陽電池セル電極の接続用シートの各部材への非接着性評価
　一つの種類のシートの同一箇所を繰り返して使用し、下記の各種部材とシートを直接接触させて接続動作をそれぞれ１０回繰り返し、各種部材への接着有無を評価した。
非接着性１：配線部材としての銅箔線
非接着性２：配線部材としてのはんだめっき銅箔線
非接着性３：セル表面の銀系バスバー集電電極
非接着性４：エポキシ系絶縁接着剤に平均粒径６μｍの表面に金めっきしたニッケル粒子を配合した導電性接着フィルム
（６）太陽電池セル電極の接続用シートの表面状態評価
　一つの種類のシートの同一箇所を繰り返して使用し、１０枚の太陽電池セルの電極への配線部材の接続を行った。そのときのシートの表面キズや光沢などの状態を目視観察・評価した。銅箔線を使用した。 [Evaluation items for connection experiment results]
(1) Evaluation of uniformity of connecting portion Total length of solar battery cell: A cross section of all connecting portions having a length of 150 mm was observed with a microscope to evaluate whether there was a uniform and defective portion. A solder plated copper foil wire was used.
(2) Passing rate of connection resistance For one type of sheet, the wiring member is connected to the electrodes of 100 solar cells, and whether or not the connection resistance between each electrode and the wiring member is at a usable level. Confirmed and evaluated the pass rate. Copper foil wire was used.
(3) Probability of cell cracking For one type of sheet, wiring members were connected to the electrodes of 100 solar cells, and the probability of cell cracking was evaluated. Copper foil wire was used.
(4) Heating of apparatus and evaluation of dirt on pressure member surface For one type of sheet, wiring members are connected to electrodes of 100 solar cells, and dirt on the surface of heating and pressure member is evaluated. did. A solder plated copper foil wire was used.
(5) Evaluation of non-adhesiveness to each member of connecting sheet of solar battery cell electrode The same part of one kind of sheet is repeatedly used, and the following various members and the sheet are brought into direct contact with each of the connecting operations. Repeatedly, the presence or absence of adhesion to various members was evaluated.
Non-adhesiveness 1: Copper foil wire non-adhesiveness as a wiring member 2: Solder-plated copper foil wire non-adhesiveness as a wiring member 3: Silver-based bus bar collector electrode non-adhesiveness on the cell surface 4: Epoxy insulating adhesive Conductive adhesive film in which gold-plated nickel particles are blended on the surface with an average particle size of 6 μm (6) Surface condition evaluation of solar cell electrode connection sheet The same part of one type of sheet is used repeatedly and 10 The wiring member was connected to the electrodes of the single solar battery cell. The state of the sheet such as surface scratches and gloss was visually observed and evaluated. Copper foil wire was used.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１～１１の本発明の太陽電池セル電極の接続用シートを使用して、太陽電池セルの電極と配線部材とを、導電性接着材料を介して加熱及び加圧して接続することで、被加熱・加圧部全面を均一な温度・圧力で圧着できることから接点不良がなく、確実な接続が可能となり、セルの割れの発生も抑えることができることがわかる。特に、最適化したシリコーンゴムシート又はその積層品は、シートの劣化も少なく、良好な耐久性を示した。 By using the solar cell electrode connection sheet of Examples 1 to 11 of the present invention, by connecting the solar cell electrode and the wiring member by heating and pressurizing via a conductive adhesive material, It can be seen that since the entire surface of the heated / pressurized part can be pressure-bonded at a uniform temperature and pressure, there is no contact failure, reliable connection is possible, and the occurrence of cell cracking can be suppressed. In particular, the optimized silicone rubber sheet or the laminate thereof showed little durability and good durability.
　１　シリコン基板
　２　電極
　３　導電性接着材料
　４　配線部材
　５　電極接続用シート
　６　加熱・加圧部材
　１０　太陽電池セル DESCRIPTION OF SYMBOLS 1 Silicon substrate 2 Electrode 3 Conductive adhesive material 4 Wiring member 5 Electrode connection sheet 6 Heating / pressurizing member 10 Solar cell

Claims (24)

  1. 　太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に介在させて使用するポリマーシートであることを特徴とする太陽電池セル電極の接続用シート。 Polymer used by interposing between the heating and pressure member and the wiring member when connecting the electrode and wiring member for taking out the electric power of the solar cell by heating and pressing the conductive adhesive material. A sheet for connecting solar cell electrodes, characterized by being a sheet.
  2. 　前記ポリマーシートが、耐熱性樹脂、フッ素ゴム及びシリコーンゴムから選択される１種以上を含む請求項１記載の太陽電池セル電極の接続用シート。 The solar cell electrode electrode connection sheet according to claim 1, wherein the polymer sheet contains one or more selected from a heat-resistant resin, fluororubber and silicone rubber.
  3. 　前記耐熱性樹脂が、ガラス転移温度が２００℃以上又は融点が３００℃以上であるフッ素樹脂及びポリアミド系樹脂から選択される１種以上である請求項２記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to claim 2, wherein the heat-resistant resin is at least one selected from a fluororesin and a polyamide-based resin having a glass transition temperature of 200 ° C or higher or a melting point of 300 ° C or higher.
  4. 　前記ポリマーシートが、無機物及び／又は耐熱性樹脂からなるクロス及び／又は繊維で補強されてなる請求項１～３のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 3, wherein the polymer sheet is reinforced with a cloth and / or fiber made of an inorganic material and / or a heat-resistant resin.
  5. 　前記ポリマーシートが、金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び炭素の同素体から選択される１種以上の無機物からなる熱伝導性充填剤を含有する請求項１～４のいずれか１項記載の太陽電池セル電極の接続用シート。 The polymer sheet contains a thermally conductive filler made of one or more inorganic substances selected from metals, metal oxides, metal nitrides, metal carbides, metal hydroxides, and carbon allotropes. The sheet | seat for a connection of the photovoltaic cell electrode of any one of these.
  6. 　前記ポリマーシートが、
    （Ａ）平均重合度が１００以上である架橋性オルガノポリシロキサン：１００質量部、
    （Ｂ）金属、金属酸化物、金属窒化物、金属炭化物、金属水酸化物及び炭素の同素体から選択される少なくとも１種の熱伝導性粉末：０～６００質量部、
    （Ｃ）カーボンブラック粉末：０～８０質量部、
    （Ｄ）ＢＥＴ比表面積が５０ｍ2／ｇ以上である補強性シリカ粉末：０～５０質量部
    及び、
    （Ｅ）硬化剤：硬化有効量
    を含むシリコーンゴム組成物をシート状に成形して加熱硬化させてなるシリコーンゴムシートである請求項１～５のいずれか１項記載の太陽電池セル電極の接続用シート。     The polymer sheet is
    (A) Crosslinkable organopolysiloxane having an average degree of polymerization of 100 or more: 100 parts by mass,
    (B) at least one heat conductive powder selected from metal, metal oxide, metal nitride, metal carbide, metal hydroxide and carbon allotrope: 0 to 600 parts by mass;
    (C) Carbon black powder: 0 to 80 parts by mass,
    (D) Reinforcing silica powder having a BET specific surface area of 50 m 2 / g or more: 0 to 50 parts by mass;
    The solar cell electrode connection according to any one of claims 1 to 5, wherein (E) a curing agent is a silicone rubber sheet obtained by forming a silicone rubber composition containing an effective amount of curing into a sheet and curing it by heating. Sheet.
  7. 　（Ｂ）成分である熱伝導性粉末が、５質量部以上配合され、平均粒径１～５０μｍの金属ケイ素粉末である請求項６記載の太陽電池セル電極の接続用シート。 7. The solar cell electrode connecting sheet according to claim 6, wherein the thermal conductive powder as component (B) is a metallic silicon powder having an average particle size of 1 to 50 μm, blended in an amount of 5 parts by mass or more.
  8. 　上記金属ケイ素粉末が、表面に強制酸化膜が形成されてなる請求項７記載の太陽電池セル電極の接続用シート。 The solar cell electrode electrode connection sheet according to claim 7, wherein a forced oxide film is formed on the surface of the metal silicon powder.
  9. 　（Ｂ）成分である熱伝導性粉末が、５質量部以上配合され、平均粒径１～５０μｍの結晶性二酸化ケイ素粉末である請求項６記載の太陽電池セル電極の接続用シート。 The connection sheet for solar cell electrodes according to claim 6, wherein the thermal conductive powder as component (B) is a crystalline silicon dioxide powder containing 5 parts by mass or more and having an average particle size of 1 to 50 µm.
  10. 　前記シリコーンゴムシートの２３℃における切断時伸びが４０～１，０００％、タイプＡデュロメーターでの硬さが１０～９０である請求項６～９のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection according to any one of claims 6 to 9, wherein the silicone rubber sheet has an elongation at break at 23 ° C of 40 to 1,000% and a hardness with a type A durometer of 10 to 90. Sheet.
  11. 　熱伝導率が０．３Ｗ／ｍＫ以上である請求項１～１０のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode electrode connecting sheet according to any one of claims 1 to 10, wherein the thermal conductivity is 0.3 W / mK or more.
  12. 　請求項２～１１のいずれか１項記載のポリマーシートから選択される２種以上のシートを積層させてなる請求項１記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to claim 1, wherein two or more kinds of sheets selected from the polymer sheets according to any one of claims 2 to 11 are laminated.
  13. 　厚さが０．０１～１ｍｍである請求項１～１２のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 12, wherein the sheet has a thickness of 0.01 to 1 mm.
  14. 　前記配線部材が、帯状の導電性部材である請求項１～１３のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 13, wherein the wiring member is a strip-shaped conductive member.
  15. 　前記配線部材が、Ｃｕ，Ａｇ，Ａｕ，Ｆｅ，Ｎｉ，Ｚｎ，Ｃｏ，Ｔｉ，Ｐｂ及びＭｇからなる群より選択される１種以上の金属元素を含む請求項１～１４のいずれか１項記載の太陽電池セル電極の接続用シート。 15. The wiring member according to claim 1, wherein the wiring member includes one or more metal elements selected from the group consisting of Cu, Ag, Au, Fe, Ni, Zn, Co, Ti, Pb, and Mg. Sheet for connecting solar cell electrodes.
  16. 　前記配線部材が、はんだで被覆されてなる請求項１～１５のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 15, wherein the wiring member is coated with solder.
  17. 　前記導電性接着材料が、絶縁性樹脂及び導電性粒子を含有する導電性樹脂接着剤である請求項１～１６のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 16, wherein the conductive adhesive material is a conductive resin adhesive containing an insulating resin and conductive particles.
  18. 　前記導電性接着材料が、フィルム状である請求項１～１７のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 17, wherein the conductive adhesive material is in the form of a film.
  19. 　前記導電性接着材料が、はんだである請求項１～１６のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 16, wherein the conductive adhesive material is solder.
  20. 　前記導電性接着材料が、配線部材上に形成されてなる請求項１～１９のいずれか１項記載の太陽電池セル電極の接続用シート。 The solar cell electrode connection sheet according to any one of claims 1 to 19, wherein the conductive adhesive material is formed on a wiring member.
  21. 　太陽電池セルの電力を取り出すための電極と配線部材とを導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に請求項１～２０のいずれか１項記載の接続用シートを介在させて加熱及び加圧することを特徴とする太陽電池モジュールの製造方法。 The electrode for taking out the electric power of the solar battery cell and the wiring member are connected by heating and pressing the conductive adhesive material between the heating and pressing member and the wiring member. A method for manufacturing a solar cell module, comprising heating and pressurizing the sheet for connection according to any one of the preceding claims.
  22. 　太陽電池セル表面に設けられた電力を取り出すための表面電極及び裏面電極と配線部材とをそれぞれ導電性接着材料を介して加熱及び加圧して接続するに際し、加熱及び加圧部材と上記配線部材との間に請求項１～２０のいずれか１項記載の接続用シートを介在させて、上記表面電極及び裏面電極と上記配線部材とをそれぞれ同時に加熱及び加圧して接続する請求項２１記載の太陽電池モジュールの製造方法。 When connecting the surface electrode and the back electrode for taking out electric power provided on the surface of the solar battery cell and the wiring member by heating and pressing through the conductive adhesive material, respectively, the heating and pressing member and the wiring member The solar cell according to claim 21, wherein the connection sheet according to any one of claims 1 to 20 is interposed between the front electrode, the rear electrode, and the wiring member by simultaneously heating and pressurizing the solar cell. Manufacturing method of battery module.
  23. 　太陽電池セルの電力を取り出すための電極と配線部材が接続された単一の太陽電池セルで構成される太陽電池モジュールであって、請求項２１又は２２記載の製造方法によって得られることを特徴とする太陽電池モジュール。 It is a solar cell module comprised by the single solar cell connected with the electrode and wiring member for taking out the electric power of a photovoltaic cell, Comprising: It is obtained by the manufacturing method of Claim 21 or 22 characterized by the above-mentioned. Solar cell module.
  24. 　請求項２３記載の太陽電池セルが複数配列され、互いに隣接する前記太陽電池セルの電力を取り出すための電極が配線部材により接続されていることを特徴とする太陽電池モジュール。 25. A solar cell module, wherein a plurality of solar cells according to claim 23 are arranged, and electrodes for taking out electric power of the solar cells adjacent to each other are connected by a wiring member.
PCT/JP2010/053604 2009-03-11 2010-03-05 Connection sheet for solar battery cell electrode, process for manufacturing solar cell module, and solar cell module WO2010103998A1 (en)

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MY157233A (en) 2016-05-13
KR20110133605A (en) 2011-12-13

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